Dishwasher Detergent

ABSTRACT

The invention relates to a solid dishwasher detergent which comprises a) 1 to 40 wt. % of a bleaching agent, b) 0.25 to 20 wt. % of non-ionic surfactants(s); and c) 0.01 to 10 wt. % of at least one polymer having a molar mass of 2000 gmol −1  or more and having at least one positive charge. The detergent is characterized in that the weight ratio of component b) to component c) ranges between 25:1 and 100:1, preferably between 30:1 and 80:1, and specifically between 35:1 and 75:1. The inventive dishwasher detergent is characterized by an improved cleaning and rinsing power and improved processability and shelf life.

This application relates to detergent or cleansing agents. Inparticular, this application relates to polymer-containing andsurfactant-containing detergents or cleansing agents.

Nowadays, more stringent standards are often posed for machine-washedcrockery than for hand washed crockery. Accordingly, crockery totallycleaned of food residues is also not considered faultless if, after theautomatic dishwashing, it still has whitish spots from hard water orother mineral salts that originate from dried-out water droplets becauseof the lack of wetting agents.

In order to obtain shining and spotless crockery, rinsing agents aretherefore employed with success today. The addition of rinsing agents atthe end of the washing program ensures that the water almost totallyruns off the washed goods, such that the various surfaces are free ofresidues and immaculately spotless at the end of the washing program.

Automatic dishwashing of tableware in household dishwashers normallyincludes a prewash cycle, a main wash cycle and a rinse cycle, that areinterrupted by intermediate wash cycles. For the majority of machines,the prewash cycle is selectable for heavily soiled crockery, however, itis only selected in exceptional cases by the user, such that in themajority of cases a main wash cycle, an intermediate wash cycle withclean water and a rinse cycle are carried out. The temperature of themain wash cycle varies between 40 and 65° C. depending on the machinetype and program choice. In the rinse cycle, rinse agents that usuallycomprise non-ionic surfactants as the major constituent are added from adosing tank into the machine. These rinse agents are in liquid form andare extensively described in the prior art. Their function is primarilyto prevent lime deposits and coatings on the cleaned crockery. Inaddition to water and weakly foaming non-ionic surfactants, these rinseagents also frequently comprise hydrotropes, pH adjusters, such ascitric acid, or deposition-inhibiting polymers.

From EP-B1 0 197 434 (Henkel), liquid rinse agents are known thatcomprise mixed ethers as the non-ionic surfactants. A plurality ofdifferent materials (glass, metal, silver, plastic, porcelain) iscleaned in the dishwasher. All these materials have to be provided withthe best possible wetting in the rinsing cycle. Rinse formulations thatonly comprise mixed ethers as the surfactant components do not satisfythese requirements—or only to a limited extent—with the result that therinsing or drying effect is unsatisfactory, particularly for plasticsurfaces.

The reservoir in the dishwasher has to be regularly filled up with rinseagent, one filling being sufficient for 10 to 50 wash cycles, dependingon the type of machine. Forgetting to fill up the tank particularlyresults in unsightly glasses due to lime deposits and coatings.Consequently, there exist several proposals in the prior art to solvethis by integrating a rinse agent in the cleansing agent for automaticdishwashers. These proposals are linked to the presentation form of thecompact molded body.

Thus, the European Patent application EP-A-0 851 024 (Unilever)describes two-layer cleansing agent tablets, whose first layer comprisesperoxy bleaching agents, builders and enzymes, while the second layercomprises acidifiers and a continuous medium with a melting pointbetween 55 and 70° C. as well as deposition inhibitors. Thehigh-melting, continuous medium is intended to provide a delayed releaseof the acid(s) and deposition inhibitor(s) and realize a rinsing effect.Dishwasher detergents in powder form or surfactant-containing rinsesystems are not mentioned in this publication.

The object of the present invention consists of the provision ofbleaching agent-containing dishwasher detergents with a rinse function,which deliver at least the same results in regard to the applicationtechnological properties as standard rinse agents and which moreoveryield additional performance advantages. In this regard, the noveldishwasher detergents should develop their cleansing and rinsingperformance independently of the preparation form, in particular withoutthe addition of high-melting additives. In addition, the noveldishwasher detergents should excel in their improved shelf life andprocessability in comparison with conventional agents.

It has now been discovered that above average cleansing and rinsingresults are delivered by bleaching agent-containing cleansing agentsthat comprise non-ionic surfactants and polymers with positively chargedmonomer units as additional constituents, the non-ionic surfactants andthe mentioned polymers being present in these agents in a defined weightratio.

Accordingly, the subject matter of the present application is a soliddishwasher detergent comprising

-   -   (a) 1 to 40 wt. % bleaching agent,    -   (b) 0.25 to 20 wt. % non-ionic surfactant(s);    -   (c) 0.01 to 10 wt. % of at least one polymer with a molecular        weight of 2000 gmol⁻¹ or greater that possesses at least one        positive charge,

wherein the weight ratio of the component b) to component c) is between25:1 and 100:1, preferably between 30:1 and 80:1 and particularlybetween 35:1 and 75:1.

A first important constituent of the inventive solid dishwasherdetergent is the bleaching agent. Among the compounds, which serve asbleaches and liberate H₂O₂ in water, sodium percarbonate, sodiumperborate tetrahydrate and sodium perborate monohydrate are ofparticular importance. Examples of further bleaching agents that may beused are peroxypyrophosphates, citrate perhydrates and H₂O₂-liberatingperacidic salts or peracids, such as perbenzoates, peroxyphthalates,diperoxyazelaic acids, phthaloimino peracids or diperoxydodecanediocacids. Inventive cleansing agents can also comprise bleaching agentsfrom the group of the organic bleaching agents. Typical organicbleaching agents are the diacyl peroxides, such as e.g. dibenzoylperoxide. Further typical organic bleaching agents are the peroxy acids,wherein the alkylperoxy acids and the arylperoxy acids may be named asexamples. Preferred representatives that can be added are (a)peroxybenzoic acid and ring-substituted derivatives thereof, such asalkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid andmagnesium monoperphthalate, (b) aliphatic or substituted aliphaticperoxy acids, such as peroxylauric acid, peroxystearic acid,ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)],o-carboxybenzamido peroxycaproic acid, N-nonenylamido peradipic acid andN-nonenylamido persuccinates and (c) aliphatic and araliphaticperoxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid,1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,the diperoxyphthalic acids, 2-decyidiperoxybutane-1,4-dioic acid,N,N-terephthaloyl-di(6-aminopercaproic acid).

Chlorine- or bromine-releasing substances can also be incorporated asthe bleaching agents into the inventive dispersions. Suitable chlorine-or bromine-releasing materials include, for example, heterocyclicN-bromamides and N-chloramides, for example trichloroisocyanuric acid,tribromoisocyanuric acid, dibromoisocyanuric acid and/ordichloroisocyanuric acid (DICA) and/or salts thereof with cations suchas potassium and sodium. Hydantoin compounds, such as1,3-dichloro-5,5-dimethyl hydantoin, are also suitable.

In the context of the present application, a particularly preferreddishwasher detergent according to the invention comprises preferably 2.5to 30 wt. %, particularly preferably 3.5 to 20 wt. % and particularly 5to 15 wt. % bleaching agent, preferably sodium percarbonate.

The active oxygen content of the dishwasher detergents according to theinvention, based on the total weight of the detergent, preferably rangesbetween 0.4 and 10 wt. %, particularly preferably between 0.5 and 8 wt.% and particularly between 0.6 and 5 wt. %. Particularly preferredprocessed solid detergents possess an active oxygen content above 0.3wt. %, preferably above 0.7 wt. %, particularly preferably above 0.8 wt.% and particularly above 1.0 wt. %.

A second important constituent of the dishwasher detergent according tothe invention is the non-ionic surfactant. As described previously, theinventive agents comprise between 0.25 and 20 wt. % non-ionicsurfactant(s). However, in the context of the present application,preferred agents are those that comprise the non-ionic surfactant(s) inquantities between 0.5 to 15 wt. %, preferably from 1 to 12.5 wt. %,particularly preferably from 1.5 to 10 wt. % and particularly from 2 to8 wt. %. Preferably however, the inventive agents comprise more than 2.0wt. % non-ionic surfactant(s), particularly between 2.5 and 7 wt. %,particularly preferably between 3.0 and 6 wt. % and especially between3.0 and 5.5 wt. %.

In the scope of the present application, all non-ionic surfactants knownto the person skilled in the art may be used as the non-ionicsurfactants, in so far as they are fundamentally suitable for mixingwith bleaching agents. Preferred non-ionic surfactants are alkoxylated,advantageously ethoxylated, particularly primary alcohols preferablycontaining 8 to 18 carbon atoms and, on average, 1 to 12 moles ofethylene oxide (EO) per mole of alcohol, in which the alcohol group maybe linear or, preferably, methyl-branched in the 2-position or maycontain linear and methyl-branched groups in the form of the mixturestypically present in oxoalcohol groups. Particularly preferred are,however, alcohol ethoxylates with linear groups from alcohols of naturalorigin with 12 to 18 carbon atoms, e.g. from coco-, palm-, tallow- oroleyl alcohol, and an average of 2 to 8 EO per mole alcohol. Exemplarypreferred ethoxylated alcohols include C₁₂₋₁₄-alcohols with 3 EO or 4EO,C₉₋₁₁-alcohols with 7 EO, C₁₃₋₁₅— alcohols with 3 EO, 5 EO, 7 EO or 8EO, C₁₂₋₁₈-alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, aswell as mixtures of C₁₂₋₁₄-alcohols with 3 EO and C12-18-alcohols with 5EO. The cited degrees of ethoxylation constitute statistically averagevalues that can be a whole or a fractional number for a specificproduct. Preferred alcohol ethoxylates have a narrowed homologdistribution (narrow range ethoxylates, NRE). In addition to thesenon-ionic surfactants, fatty alcohols with more than 12 EO can also beused. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30EO or 40 EO.

Furthermore, as additional non-ionic surfactants, alkyl glycosides thatsatisfy the general Formula RO(G)_(x) can be added, where R means aprimary linear or methyl-branched, particularly 2-methyl-branched,aliphatic group containing 8 to 22 and preferably 12 to 18 carbon atomsand G stands for a glycose unit containing 5 or 6 carbon atoms,preferably glucose. The degree of oligomerization x, which defines thedistribution of monoglycosides and oligoglycosides, is any numberbetween 1.0 and 10, preferably between 1.2 and 1.4.

Another class of preferred non-ionic surfactants which may be used,either as the sole non-ionic surfactant or in combination with othernon-ionic surfactants, are alkoxylated, preferably ethoxylated orethoxylated and propoxylated fatty acid alkyl esters preferablycontaining 1 to 4 carbon atoms in the alkyl chain.

Non-ionic surfactants of the amine oxide type, for exampleN-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamidesmay also be suitable. The quantity in which these non-ionic surfactantsare used is preferably no more than the quantity in which theethoxylated fatty alcohols are used and, particularly no more than halfthat quantity.

Other suitable surfactants are polyhydroxyfatty acid amidescorresponding to the Formula,

in which RCO stands for an aliphatic acyl group with 6 to 22 carbonatoms, R¹ for hydrogen, an alkyl or hydroxyalkyl group with 1 to 4carbon atoms and [Z] for a linear or branched polyhydroxyalkyl groupwith 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Thepolyhydroxyfatty acid amides are known substances, which may normally beobtained by reductive amination of a reducing sugar with ammonia, analkylamine or an alkanolamine and subsequent acylation with a fattyacid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxyfatty acid amides also includes compoundscorresponding to the Formula

in which R is a linear or branched alkyl or alkenyl group containing 7to 12 carbon atoms, R¹ is a linear, branched or cyclic alkyl group or anaryl group containing 2 to 8 carbon atoms and R² is a linear, branchedor cyclic alkyl group or an aryl group or an oxyalkyl group containing 1to 8 carbon atoms, C₁₋₄ alkyl or phenyl groups being preferred, and [Z]is a linear polyhydroxyalkyl group, of which the alkyl chain issubstituted by at least two hydroxyl groups, or alkoxylated, preferablyethoxylated or propoxylated derivatives of that group.

[Z] is preferably obtained by reductive amination of a reduced sugar,for example glucose, fructose, maltose, lactose, galactose, mannose orxylose. The N-alkoxy- or N-aryloxy-substituted compounds may then beconverted into the required polyhydroxyfatty acid amides by reactionwith fatty acid methyl esters in the presence of an alkoxide ascatalyst.

The preferred surfactants are weakly foaming non-ionic surfactants. Theinventive detergents for automatic dishwashers are especially preferredwhen they comprise non-ionic surfactants, particularly non-ionicsurfactants from the group of alkoxylated alcohols. Preferred non-ionicsurfactants are alkoxylated, advantageously ethoxylated, particularlyprimary alcohols preferably containing 8 to 18 carbon atoms and, onaverage, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, inwhich the alcohol group may be linear or, preferably, methyl-branched inthe 2-position or may contain linear and methyl-branched groups in theform of the mixtures typically present in oxoalcohol groups.Particularly preferred are, however, alcohol ethoxylates with lineargroups from alcohols of natural origin with 12 to 18 carbon atoms, e.g.from coco-, palm-, tallow- or oleyl alcohol, and an average of 2 to 8 EOper mole alcohol. Exemplary preferred ethoxylated alcohols includeC₁₂₋₁₄-alcohols with 3 EO or 4EO, C₉₋₁₁-alcohols with 7 EO, C₁₃₋₁₅—alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂₋₁₈-alcohols with 3 EO, 5 EOor 7 EO and mixtures thereof, as well as mixtures of C₁₂₋₁₄-alcoholswith 3 EO and C₁₂₋₁₈-alcohols with 5 EO. The cited degrees ofethoxylation constitute statistically average values that can be a wholeor a fractional number for a specific product. Preferred alcoholethoxylates have a narrowed homolog distribution (narrow rangeethoxylates, NRE). In addition to these non-ionic surfactants, fattyalcohols with more than 12 EO can also be used. Examples of these aretallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In the scope of the present application, non-ionic surfactants from thegroup of alkoxylated alcohols, particularly preferably from the group ofmixed alkoxylated alcohols and especially from the group ofEO-AO-EO-non-ionic surfactants are incorporated with particularpreference.

The inventive agents are especially preferred when they comprise anon-ionic surfactant that exhibits a melting point above roomtemperature. Accordingly, preferred dishwasher agents are characterizedin that they comprise non-ionic surfactant(s) with a melting point above20° C., preferably above 25° C., particularly preferably between 25 and60° C. and, especially between 26.6 and 43.3° C.

Suitable non-ionic surfactants with a melting and/or softening point inthe cited temperature range are, for example weakly foaming non-ionicsurfactants that can be solid or highly viscous at room temperature. Ifnon-ionic surfactants are used that are highly viscous at roomtemperature, they preferably have a viscosity above 20 Pas, particularlypreferably above 35 Pas and especially above 40 Pas. Non-ionicsurfactants that have a waxy consistency at room temperature are alsopreferred.

Preferred non-ionic surfactants that are solid at room temperature areused and belong to the groups of alkoxylated non-ionic surfactants, moreparticularly ethoxylated primary alcohols, and mixtures of thesesurfactants with structurally more complex surfactants, such aspolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO)surfactants. Such (PO/EO/PO)-non-ionic surfactants are characterized inaddition as having good foam control

In one preferred embodiment of the present invention, the non-ionicsurfactant with a melting point above room temperature is an ethoxylatednon-ionic surfactant that results from the reaction of amonohydroxyalkanol or alkylphenol containing 6 to 20 carbon atoms withpreferably at least 12 moles, particularly preferably at least 15 molesand especially at least 20 moles of ethylene oxide per mole of alcoholor alkylphenol.

A particularly preferred non-ionic surfactant that is solid at roomtemperature is obtained from a straight-chain fatty alcohol containing16 to 20 carbon atoms (C₁₆₋₂₀ alcohol), preferably a C₁₈ alcohol, and atleast 12 moles, preferably at least 15 moles and more preferably atleast 20 moles of ethylene oxide. Of these non-ionic surfactants, theso-called narrow range ethoxylates (see above) are particularlypreferred.

Thus, particularly preferred dishwasher agents according to theinvention comprise ethoxylated non-ionic surfactant(s) prepared fromC₆₋₂₀-monohydroxy alkanols or C₆₋₂₀-alkyl phenols or C₁₆₋₂₀-fattyalcohols and more than 12 moles, preferably more than 15 moles andespecially more than 20 moles ethylene oxide per mole alcohol.

Preferably, the room temperature solid non-ionic surfactant additionallyhas propylene oxide units in the molecule. These PO units preferablymake up as much as 25% by weight, more preferably as much as 20% byweight and, especially up to 15% by weight of the total molecular weightof the non-ionic surfactant. Particularly preferred non-ionicsurfactants are ethoxylated monohydroxyalkanols or alkylphenols, whichhave additional polyoxyethylene-polyoxypropylene block copolymer units.The alcohol or alkylphenol component of these non-ionic surfactantmolecules preferably makes up more than 30 wt. %, more preferably morethan 50 wt. % and most preferably more than 70 wt. % of the totalmolecular weight of these non-ionic surfactants. Preferred dishwasheragents are characterized in that they comprise ethoxylated andpropoxylated non-ionic surfactants, in which the propylene oxide unitsin the molecule preferably make up as much as 25% by weight, morepreferably as much as 20% by weight and, especially up to 15% by weightof the total molecular weight of the non-ionic surfactant.

Other particularly preferred non-ionic surfactants with melting pointsabove room temperature contain 40 to 70% of apolyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blendthat contains 75% by weight of an inverted block copolymer ofpolyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and44 moles of propylene oxide and 25% by weight of a block copolymer ofpolyoxyethylene and polyoxypropylene initiated with trimethylolpropaneand containing 24 moles of ethylene oxide and 99 moles of propyleneoxide per mole of trimethylolpropane.

Non-ionic surfactants, which may be used with particular advantage areobtainable, for example, under the name of Poly Tergent® SLF-18 fromOlin Chemicals.

A further preferred inventive dishwasher agent comprises non-ionicsurfactant(s) of Formula (I)R¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)CH₂CH(OH)R²,  (1)

in which R¹ stands for a linear or branched aliphatic hydrocarbon groupwith 4 to 18 carbon atoms or mixtures thereof, R² means a linear orbranched hydrocarbon group with 2 to 26 carbon atoms or mixtures thereofand x stands for values between 0.5 and 1.5 and y stands for a value ofat least 15.

Other preferred non-ionic surfactants are the end cappedpoly(oxyalkylated) non-ionic surfactants corresponding to the followingFormulaR¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

in which R¹ and R² stand for linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30carbon atoms, R³ stands for H or for a methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x stands forvalues between 1 and 30, k and j for values between 1 and 12, preferably1 to 5. Each R³ in the above formula can be different for the case wherex≧2. R¹ and R² are preferably linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon groups containing 6 to 22carbon atoms, groups containing 8 to 18 carbon atoms being particularlypreferred. H, —CH₃ or —CH₂CH₃ are particularly preferred for the groupR³. Particularly preferred values for x are in the range from 1 to 20and more particularly in the range from 6 to 15.

As described above, each R³ in the above formula can be different forthe case where x≧2. By this means, the alkylene oxide unit in thestraight brackets can be varied. If, for example, x has a value of 3,the substituent R³ may be selected to form ethylene oxide (R³═H) orpropylene oxide (R³═CH₃) units which may be joined together in anyorder, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO),(PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x wasselected by way of example and may easily be larger, the range ofvariation increasing with increasing x-values and including, forexample, a large number of (EO) groups combined with a small number of(PO) groups or vice versa.

Particularly preferred end-capped poly(oxyalkylated) alcoholscorresponding to the above formula have values for both k and j of 1, sothat the above formula can be simplified toR¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

In this last formula, R¹, R² and R³ are as defined above and x standsfor a number from 1 to 30, preferably from 1 to 20 and especially 6 to18. Surfactants in which the substituents R¹ and R² have 9 to 14 carbonatoms, R³ stands for H and x takes a value of 6 to 15 are particularlypreferred.

In summary, preferred dishwasher detergents according to the inventionare those which comprise end capped poly(oxyalkylated) non-ionicsurfactants corresponding to the formulaR¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²in which R¹ and R² stand for linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30carbon atoms, R³ stands for H or for a methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x has a value of1 to 30, k and j have values of 1 to 12 and preferably 1 to 5, whereinsurfactants of the typeR¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²in which x stands for numbers from 1 to 30, preferably 1 to 20 andespecially 6 to 18, are particularly preferred.

Particularly preferred non-ionic surfactants in the context of thepresent invention have proved to be weakly foaming non-ionicsurfactants, Which have alternating ethylene oxide and alkylene oxideunits. Among these, the surfactants with EO-AO-EO-AO blocks are againpreferred, wherein one to ten EO or AO groups respectively are linkedtogether, before a block of the other groups follows. Inventiveautomatic dishwasher agents are preferred here, which comprisesurfactants of the general formula (II) as the non-ionic surfactant(s)

in which R¹ stands for a linear or branched, saturated or mono- orpolyunsaturated C₆₋₂₄-alkyl or alkenyl group, each group R² or R³independently of one another is selected from —CH₃, —CH₂CH₃,—CH₂CH₂—CH₃, CH(CH₃)₂, and the indices w, x, y, z independently of oneanother stand for whole numbers from 1 to 6.

The preferred non-ionic surfactants of Formula II can be manufactured byknown methods from the corresponding alcohols R¹—OH and ethylene oxideor alkylene oxide. The group R¹ in the previous Formula II can varydepending on the origin of the alcohol. When natural sources are used,the group R¹ has an even number of carbon atoms and generally is notbranched, the linear alcohols of natural origin with 12 to 18 carbonatoms, for example coconut, palm, tallow or oleyl alcohol beingpreferred. The alcohols available from synthetic sources are, forexample Guerbet alcohols or mixtures of methyl branched in the2-position or linear and methyl branched groups, as are typicallypresent in oxo alcohols. Independently of the type of alcohol added forthe manufacture of the non-ionic surfactants comprised in the agents,inventive automatic dishwasher agents are preferred, wherein R¹ inFormula II stands for an alkyl group with 6 to 24, preferably 8 to 20,particularly preferably 9 to 15 and particularly 9 to 11 carbon atoms.

In addition to propylene oxide, especially butylene oxide can be thealkylene oxide unit that alternates with the ethylene oxide unit in thepreferred non-ionic surfactants. However, also other alkylene oxides aresuitable, in which R² or R³ independently of one another are selectedfrom —CH₂CH₂CH₃ or CH(CH₃)₂. Preferred automatic dishwasher agents arethose wherein R² or R³ stand for a —CH₃ group, w and x independently ofone another stand for values of 3 or 4 and y and z independently of oneanother stand for values of 1 or 2.

In summary, especially preferred inventive non-ionic surfactants for usein the agents according to the invention are those that have aC₉₋₁₅-alkyl group with 1 to 4 ethylene oxide units, followed by 1 to 4propylene oxide units, followed by 1 to 4 ethylene oxide units, followedby 1 to 4 propylene oxide units. These surfactants exhibit the requiredlow viscosity in aqueous solution and according to the invention areused with particular preference.

Other preferred non-ionic surfactants are the end-cappedpoly(oxyalkylated) non-ionic surfactants corresponding to the followingFormula (III)R¹O[CH₂CH(R³)O]_(x)R²  (III)in which R¹ stands for linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, R²for linear or branched, saturated or unsaturated, aliphatic or aromatichydrocarbon groups with 1 to 30 carbon atoms, which preferably contains1 to 5 hydroxyl groups and preferably is also functionalized with anether group, R³ stands for H or for a methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x has a valuebetween 1 and 40

Dishwasher detergents that comprise non-ionic surfactants of the generalformulaR¹O[CH₂CH(R³)O]_(x)R²in which R¹ stands for linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms, R²for linear or branched, saturated or unsaturated, aliphatic or aromatichydrocarbon groups with 1 to 30 carbon atoms, which preferably contains1 to 5 hydroxyl groups and preferably is also functionalized with anether group, R³ stands for H or for a methyl, ethyl, n-propyl,isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, and x has a valuebetween 1 and 40, are also particularly preferred.

In particularly preferred non-ionic surfactants according to the aboveFormula (III), R³ stands for H. For the resulting end cappedpolyoxyalkylated non-ionic surfactants of Formula (IV)R¹O[CH₂CH₂O]_(x)R²  (IV)such non-ionic surfactants are particularly preferred, in which R¹stands for linear or branched, saturated or unsaturated, aliphatic oraromatic hydrocarbon groups with 1 to 30 carbon atoms, preferably with 4to 20 carbon atoms, R² for linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon groups with 1 to 30 carbon atoms,which preferably contains 1 to 5 hydroxyl groups and x has a value of 1to 40

Particularly preferred end capped polyoxyalkylated non-ionic surfactantsare those according to Formula (V)R¹O[CH₂CH₂O]_(x)CH₂CH(OH)R²  (V)which in addition to a group R¹ that stands for linear or branched,saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, comprises alinear or branched, saturated or unsaturated, aliphatic or aromatichydrocarbon group with 1 to 30 carbon atoms R² that is neighboring anintermediate group —CH₂CH(OH)—. In this Formula, x stands for a numberbetween 1 and 40.

In the scope of the present application, such dishwasher detergents areparticularly preferred that comprise non-ionic surfactant(s) of thegeneral formulaR¹O[CH₂CH₂O]_(x)CH₂CH(OH)R²which in addition to a group R¹ that stands for linear or branched,saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, additionallycomprises a linear or branched, saturated or unsaturated, aliphatic oraromatic hydrocarbon group with 1 to 30 carbon atoms R² that isneighboring a monohydroxylated intermediate group —CH₂CH(OH)— and inwhich x stands for a number between 1 and 40.

The corresponding end capped polyoxyalkylated non-ionic surfactants ofthe previous formula can be obtained, for example, by treating aterminal epoxide of the formula R²CH(O)CH₂ with an ethoxylated alcoholof the formulaR¹O[CH₂CH₂O]_(x−1)CH₂CH₂OH

Further particularly preferred surfactants are those end cappedpolyoxyalkylated non-ionic surfactants of formula (VI)R¹O[CH₂CH₂O]_(x)[CH₂CH(CH₃)O]_(y)CH₂CH(OH)R²  (VI)in which R¹ and R² independently of one another stand for linear orbranched, saturated or mono- or polyunsaturated hydrocarbon groups with2 to 26 carbon atoms, R³ independently of each other is selected from—CH₃, —CH₂CH₃, —CH₂CH₂—CH₃, CH(CH₃)₂, preferably —CH₃, however, and xand y independently of one another stand for values between 1 and 32,wherein surfactants with values for x from 15 to 32 and y from 0.5 and1.5 are quite particularly preferred.

Preferred dishwasher detergent comprise a non-ionic surfactant(s) of thegeneral formula

in which R¹ and R² independently of one another stand for linear orbranched, saturated or mono- or polyunsaturated hydrocarbon groups with2 to 26 carbon atoms and x and y independently of one another stand forvalues between 1 and 32, wherein surfactants with values for x from 15to 32 and y from 0.5 and 1.5 are quite particularly preferred.

The cited carbon chain lengths and degrees of ethoxylation oralkoxylation of the abovementioned non-ionic surfactants constitutestatistically average values that can be a whole or a fractional numberfor a specific product. Due to the manufacturing process, commercialproducts of the cited formulas do not consist in the main of one solerepresentative, but rather are a mixture, wherein not only the carbonchain lengths but also the degrees of ethoxylation or alkoxylation canbe average values and thus be fractional numbers.

Of course, the dishwasher detergents according to the invention cancomprise the abovementioned non-ionic surfactants not only as singlesubstances, but also as surfactant mixtures of two, three, four or moresurfactants. Accordingly, surfactant mixtures do not refer to mixturesof non-ionic surfactants that as a whole fall under one of the abovecited general formulas, but rather refer to such mixtures that comprisetwo, three, four or more non-ionic surfactants that can be described bythe different abovementioned general formulas.

If the dishwasher detergent according to the invention comprises two,three, four or more non-ionic surfactants, then the composition of thenon-ionic surfactants comprised in the agent preferably lies withinnarrow limits. If a mixture of two non-ionic surfactants (surfactant 1and surfactant 2) is employed, then the proportion by weight of theadded non-ionic surfactants to one another (weight proportion ofsurfactant 1 to surfactant 2) is advantageously between 10:1 and 1:10,preferably 8:1 and 1:8, particularly preferably between 6:1 and 1:6 andparticularly between 4:1 and 1:4.

If the dishwasher detergent according to the invention comprises two,three, four or more surfactants, then preferably at least one of thesurfactants has a content by weight above 2.0 wt. %, advantageouslyabove 3.0 wt. % and particularly above 4.0 wt. %.

The inventive agents comprise as the third important constituent 0.01 to10 wt. % of at least one polymer having a molecular weight of 2000gmol⁻¹ or above, which possesses a positive charge, dishwasherdetergents being particularly preferred that comprise 0.02 to 7.5 wt. %,preferably 0.05 to 5 wt. %, particularly preferably 0.07 to 2.5 wt. %and particularly 0.1 to 1 wt. % of at least one polymer with a molecularweight of 2000 gmol⁻¹ or more, which possesses a positive charge.

In principle, the abovementioned polymers having a positive charge canconcern cationic or amphoteric polymers. Preferred dishwasher detergentsaccording to the invention are those wherein the polymer that possessescationic monomer units concerns a cationic polymer and/or an amphotericpolymer.

In the context of the present invention, “cationic polymers” arepolymers that carry a positive charge in the polymer molecule. These canbe realized, for example, by (alkyl-) ammonium groups present in thepolymer chain or other positively charged groups. Particularly preferredcationic polymers come from the groups of the quaternized cellulosederivatives, the polysiloxanes having quaternized groups, the cationicguar derivatives, the polymeric dimethyldiallylammonium salts and theircopolymers with esters and amides of acrylic acid and methacrylic acid,the copolymers of vinyl pyrrolidone with quaternized derivatives ofdialkylamino acrylate and -methacrylate, the vinylpyrrolidone/methoimidazolinium chloride copolymers, the quaternizedpolyvinyl alcohols or the polymers listed under the INCI descriptionsPolyquaternium 2, Polyquaternium 17, Polyquaternium 18 andPolyquaternium 27.

In the context of the present invention, “amphoteric polymers” arepolymers that possess, in addition to a positively charged group in thepolymer chain, further negatively charged groups or monomer units. Thesegroups can concern, for example, carboxylic acids, sulfonic acids orphosphonic acids.

In the scope of the present application, dishwasher detergents areparticularly preferred that comprise a polymer c) that possesses monomerunits of the formula R¹R²C═CR³R⁴, in which each group R¹, R², R³, R⁴independently of each other is selected from hydrogen, derivatizedhydroxyl groups, C1 to C30 linear or branched alkyl groups, aryl, arylsubstituted C₁₋₃₀ linear or branched alkyl groups, polyalkoxylated alkylgroups, heteroatomic organic groups having at least one positive chargewithout charged nitrogen, at least one quaternized nitrogen atom or atleast one amino group with a positive charge in the pH range 2 to 11, orsalts hereof, with the proviso that at least one group R¹, R², R³, R⁴ isa heteroatomic organic group with at least one positive charge withoutcharged nitrogen, at least one quaternized nitrogen atom or at least oneamino group with a positive charge.

In the scope of the present application, particularly preferred cationicor amphoteric polymers comprise a compound of the general Formula (VII)as the monomer unit.

in which R¹ and R⁴ independently of one another stands for a linear orbranched hydrocarbon group with 1 to 6 carbon atoms; R² and R³independently of one another stand for an alkyl, hydroxyalkyl oraminoalkyl group, in which the alkyl group is linear or branched and has1 to 6 carbon atoms, wherein it is preferably a methyl group; x and yindependently of one another stand for whole numbers between 1 and 3. Xrepresents a counter ion, preferably a counter ion from the groupchloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate,lauryl sulfate, dodecylbenzene sulfonate, p-toluene sulfonate(tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate,formate, acetate or mixtures thereof.

Preferred groups R¹ and R⁴ in the above Formula (VII) are selected from—CH₃, —CH₂—CH₃, —CH₂—CH₂—C H₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH,—CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, and—(CH₂CH₂—O)_(n)H.

In the scope of the present application, quite particularly preferredpolymers possess a cationic monomer unit of the general Formula (VII),in which R¹ and R⁴ stand for H, R² and R³ stand for methyl, and x and yare each 1. The monomer units corresponding to the formulaH₂C═CH—(CH₂)—N⁺(CH₃)₂—(CH₂)—C H═CH₂ x⁻are also designated as DADMAC (diallyidimethylammonium chloride) for thecase where X=chloride.

In the scope of the present application, further particularly preferredcationic or amphoteric polymers comprise a monomer unit of the generalformulaR¹HC═CR²—C(O)—NH—(CH₂)_(x)—N⁺R³R⁴R⁵ X⁻  (VIII).in which R¹, R², R³, R⁴ and R⁵ independently of one another stand forlinear or branched, saturated or unsaturated alkyl, or hydroxyalkylgroup with 1 to 6 carbon atoms, preferably for a linear or branchedalkyl group selected from —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃,—CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃,—CH(OH)—CH₂—CH₃, and —(CH₂CH₂—O)_(n)H, and x stands for a whole numberbetween 1 and 6.

In the scope of the present application, quite particularly preferredpolymers possess a cationic monomer unit of the general Formula (VIII),in which R¹ stands for H, and R², R³, R⁴ and R⁵ stand for methyl, and xstands for 3. The monomer units corresponding to the formulaH₂C═C(CH₃)—C(O)—NH—(CH₂)_(x)—N⁻(CH₃)₃ X⁻are also designated as MAPTAC (methylacrylamidopropyl-trimethylammoniumchloride) for the case where X⁻=chloride.

According to the invention, preferred dishwasher detergents are thosewherein the polymer c) comprises diallyldimethylammonium salts and/oracrylamidopropyl-trimethylammonium salts as the monomer units.

The previously mentioned polymers possess not only cationic groups butalso anionic groups or monomer units. These anionic monomer units come,for example, from the group of the linear or branched, saturated orunsaturated carboxylates, the linear or branched, saturated orunsaturated phosphonates, the linear or branched, saturated orunsaturated sulfates or the linear or branched, saturated or unsaturatedsulfonates. Preferred monomer units are acrylic acid, the (meth)acrylicacids, the (dimethyl)acrylic acid, the (ethyl)acrylic acid, thecyanoacrylic acid, the vinylacetic acid, the allylacetic acid, thecrotonic acid, the maleic acid, the fumaric acid, the cinnamic acid andits derivatives, the allylsulfonic acids, such as for exampleallyloxybenzene sulfonic acid and methallyl sulfonic acid or theallylphosphonic acids.

Preferred usable amphoteric polymers come from the group of thealkylacrylamide/acrylic acid copolymers, the alkylacrylamide/methacrylicacid copolymers, the alkylacrylamide/methylmethacrylic acid copolymers,the alkylacrylamide/acrylic acid/alkyl-aminoalkyl(meth)acrylic acidcopolymers, the alkylacrylamide/methacrylicacid/alkylaminoalkyl(meth)acrylic acid copolymers, thealkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acidcopolymers, the alkylacrylamide/alkyl methacrylate/alkylaminoethylmethacrylate/alkyl methacrylate copolymers as well as the copolymers ofunsaturated carboxylic acids, cationic derivatized unsaturatedcarboxylic acids and optionally additional ionic or non-ionic monomers.

Preferred usable zwitterionic polymers come from the group of theacrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers as wellas their alkali- and ammonium salts the acrylamidoalkyltrialkylammoniumchloride/methacrylic acid copolymers as well as their alkali- andammonium salts and their methacroylethylbetain/methacrylate copolymers.

In addition, preferred amphoteric polymers are those that includemethacrylamidoalkyl-trialkylammonium chloride anddimethyl(diallyl)ammonium chloride as the cationic monomer in additionto one or more anionic monomers.

Particularly preferred amphoteric polymers come from the group ofmethacrylamidoalkyl-trialkylammonium chloride/dimethyl(diallyl)ammoniumchloride/acrylic acid copolymers, themethacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammoniumchloride/methacrylic acid copolymers and themethacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammoniumchloride/alkyl(meth)acrylic acid copolymers as well as their alkali- andammonium salts.

In particular, preferred amphoteric polymers are from the group of themethacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammoniumchloride/acrylic acid copolymers, themethacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammoniumchloride/acrylic acid copolymers and themethacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammoniumchloride/alkyl(meth)acrylic acid copolymers as well as their alkali- andammonium salts.

In a particularly preferred embodiment of the present invention, thepolymers with a molecular weight of 2000 gmol⁻¹ or above that arecomprised in the inventive agents are present in preconditioned form.Suitable preconditioning of the polymers include

-   -   Encapsulation of the polymers by water-soluble or        water-dispersible coating agents, preferably by water-soluble or        water-dispersible natural or synthetic polymers;    -   Encapsulation of the polymers by water-insoluble, meltable        coating agents, preferably by water-insoluble coating agents        from the group of the waxes or paraffins having a melting point        above 30° C.;    -   Cogranulation of the polymers with inert carriers, preferably        with carriers from the group of detergent active or cleansing        active substances, particularly preferably from the group of        builders or cobuilders.

In a preferred dishwasher detergent the proportion by weight of thecomponent b) to the component c) is between 25:1 and 100:1, preferablybetween 28:1 and 90:1, particularly preferably between 33:1 and 80:1 andespecially between 35:1 and 70:1.

The inventive solid dishwasher detergents can be offered to the consumerin different preconditioned forms. In addition to the known powders,granules or extrudates, preferred dishwasher detergents in the scope ofthe present application are offered to the consumer in the form ofpreconditioned unit doses. The group of these preconditioned unit dosesincludes, for example, the mono or multiphase compacted solids(preferably mono or multi phase tablets), mono or multiphase castings,or filled, water-soluble or water-dispersible containers, preferablyfilled water-soluble or water-dispersible injection moldings, deep drawnobjects or filled film pouches.

A further preferred embodiment of the present application relates toinventive dishwasher detergents in the form of a preconditioned unitdose, wherein said preconditioned unit dose concerns a molded body,preferably a multiphase molded body, in particular a multiphase tabletwith a filled cavity.

In the scope of the present application, “deep drawn objects” aredesignated as those containers that are obtained by deep drawing anenvelope material from a film. The “deep drawing” process in thiscontext involves processes, in which a film of coating material, afterbeing placed over a receiving cavity in a deep-drawing mold, is moldedby the action of pressure and/or vacuum. The external coating materialcan be treated before or during the shaping by the action of heat and/orsolvents and/or conditioning by relative humidities and/or temperatures,modified with respect to the surrounding conditions. The application ofpressure can occur by means of two parts of a tool, which fit positivelyand negatively with each other and shape the film brought between thesetools by pressing them together. The use of compressed air and/or theinherent weight of the film and/or the inherent weight of an activesubstance placed on the upper side of the film, is/are also suitable aspressure forces.

After the deep drawing, the deep-drawn external coating materials arepreferably fixed in their deep-drawn shape by applying a vacuum insidethe receiving cavity. The vacuum is preferably applied continuously fromdeep drawing to filling, preferably to sealing and particularly up tothe separation from the receiving chamber. It is also possible to applya discontinuous vacuum, for example up to the deep drawing of thereceiving chambers and (after a pause) before and during the filling ofthe receiving chamber. The continuous or discontinuous vacuum can alsovary in strength; for example at the beginning of the process (deepdrawing of the film), higher values can be applied than at the end(filling or sealing or separation).

As already mentioned, the external coating material can be treated priorto or during the shaping into the receiving cavity of the mold by theaction of heat. Thus the external coating material, preferably awater-soluble or water-dispersible polymer film, is heated for up to 5seconds, advantageously for 0.1 to 4 seconds, particularly preferablyfor 0.2 to 3 seconds and in particular for 0.4 to 2 seconds to atemperature above 60° C., advantageously above 80° C., particularlypreferably between 100 and 120° C. and particularly to temperaturesbetween 105 and 115° C. To dissipate this heat, but particularly to alsodissipate the heat brought into the receiving chamber by the deep drawnproduct (e.g. melts), it is preferred to cool the matrix and thereceiving cavity in this matrix. They are advantageously cooled down totemperatures below 20° C., preferably below 15° C., particularlypreferably to temperatures between 2 and 14° C. and particularly totemperatures between 4 and 12° C. Preferably, the cooling is continuousfrom the start of the deep drawing process to the sealing and separationfrom the receiving chamber. Liquid coolants are particularly suitablefor cooling; preferably water, which is circulated inside the matrix bymeans of special cooling ducts.

This cooling, like the previously described, continuous or discontinuousapplication of a vacuum, has the advantage of preventing a shrink-backof the deep drawn containers, whereby not only the optical properties ofthe product are improved, but also the material, filled in the receivingchamber, is simultaneously prevented from escaping past the edge of thereceiving chamber, e.g. into the sealing area of the chamber. Sealingproblems with filled chambers are thus avoided.

The deep drawing process can be sub-divided into two methods, one inwhich the external coating material is fed horizontally in a mold andfrom there fed horizontally to filling and/or sealing and/or removal,and processes, in which the external coating material is fed over acontinuously circulating matrix shaping roll (optionally with acounter-running stamping shaping roll, which leads the upper shapingstamps into the cavities of the matrices' shaping roll). The firstmentioned process variant, the flatbed process, is carried out bothcontinuously and discontinuously, the second process variant with theshaping rolls is usually continuous. All known deep drawing processesare suitable for manufacturing the preferred agents according to theinvention. The receiving cavities in the matrices can be arranged “inline” or offset.

The deep drawn objects can have one, two, three or more chambers. Thesechambers in the deep drawn part can be arranged beside one anotherand/or above one another. In a preferred embodiment of the presentapplication, the inventive dishwasher detergent is conditioned in awater-soluble or water-dispersible deep drawn object that also comprisesa cleansing agent or mixture of cleansing agents in liquid or gel form,in addition to the inventive solid dishwasher detergent present in aseparate chamber.

The water-soluble or water-dispersible containers can also bemanufactured by injection molding as well as by deep drawing.Injection-molding means converting a molding material in such a way thatmaterial required for more than one injection cycle is heated in abarrel to soften it and is then introduced, under pressure, through anozzle into the cavity of an already closed mold. The process isprincipally used for non-crosslinkable molding materials, which cooldown in the mold and solidify. Injection molding is a very efficientmodern process for manufacturing non-cut objects and is particularlysuitable for automated mass-production. In practical operation, thethermoplastic molding materials (powder, pellets, diced forms, pastes,inter alia) are heated until liquid (to 180° C.) and injected under highpressure (up to 140 MPa) into a preferably water-cooled closed,two-piece mold, consisting of a cavity (earlier a matrix) and core(earlier stamp), where they cool and solidify. Plunger and screwinjection molding machines are suitable. Water-soluble polymers, such asthe abovementioned cellulose ethers, pectins, polyethylene glycols,polyvinyl alcohols, polyvinyl pyrrolidones, alginates, gelatines orstarches are suitable molding materials (injection molding materials).

However, the external coating materials can also be cast into moldings.The molding of the resulting inventive preferred water-soluble orwater-dispersible portioned agent includes at least one solidified melt.This melt can be a molten pure substance or a mixture of severalsubstances. Naturally, it is possible to mix the individual substancesbefore melting into a multi-substance melt, or to prepare separatemelts, which are then combined. Melts of mixtures of substances can beadvantageous, e.g. if eutectic mixtures form, which melt much lower andtherefore reduce process costs.

In a preferred embodiment of the present invention, the exterior coatingmaterial cast into the molding includes at least partially an inventivedetergent or cleansing agent. It is particularly preferred tomanufacture cast moldings, which consist entirely of an inventivedetergent or cleansing agent.

Dishwasher detergents in a preconditioned unit dose, wherein thepreconditioned unit dose concerns a filled, water-soluble container,preferably a filled injection molded object, a filled casting or afilled film pouch are particularly preferred in the scope of the presentapplication.

The preconditioned unit doses described above preferably concern unitdoses for a single application. In order to be able to also add the unitdoses through the dosing chamber of the dishwasher, their volume isadvantageously below 25 ml, preferably between 10 and 25 ml,particularly preferably between 12 and 23 and particularly between 15and 21 ml. The weight of these preconditioned unit doses preferablyranges between 10 and 30 g, particularly preferably between 13 and 27 gand particularly between 16 and 24 g. Dishwasher detergents in the formof a preconditioned unit dose that comprises between 0.5 and 4 g,preferably between 0.8 and 3.5 g, particularly preferably between 1.0and 3.0 g and particularly between 1.5 and 2.5 g of non-ionicsurfactants are particularly preferred in the scope of the presentapplication.

The inventive solid dishwasher detergents are particularly suitable forcleaning glassware. Accordingly, a further subject matter of the presentapplication is the use of the inventive dishwasher detergents forcleaning and rinsing glassware.

In addition to the abovementioned bleaching agents, non-ionicsurfactants and polymers, the inventive dishwasher detergents preferablycomprise additional active detergent and cleansing substances,particularly active detergent and cleansing substances from the group ofthe bleach activators, polymers, builders, surfactants, enzymes,disintegration aids, electrolytes, pH adjustors, fragrances, perfumecarriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors andglass-corrosion inhibitors.

Builders

In the context of the present invention, the builders include especiallythe zeolites silicates, carbonates, organic co builders and also—wherethere are no ecological reasons preventing their use—phosphates.

Suitable crystalline, layered sodium silicates correspond to the generalformula NaMSi_(x)O2_(x+1).H₂O, wherein M is sodium or hydrogen, x is anumber from 1.9 to 4 and y is a number from 0 to 20, preferred valuesfor x being 2, 3 or 4. Preferred crystalline layered silicates of thegiven formula are those in which M stands for sodium and x assumes thevalues 2 or 3. Both β- and δ-sodium disilicates Na₂Si₂O₅.yH₂O arepreferred.

Other useful builders are amorphous sodium silicates with a modulus(Na₂O:SiO₂ ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and morepreferably 1:2 to 1:2.6, which dissolve with a delay and exhibitmultiple wash cycle properties. The delay in dissolution compared withconventional amorphous sodium silicates can have been obtained invarious ways, for example by surface treatment, compounding,compressing/compacting or by over-drying. In the context of thisinvention, the term “amorphous” also means “X-ray amorphous”. In otherwords, the silicates do not produce any of the sharp X-ray reflexionstypical of crystalline substances in X-ray diffraction experiments, butat best one or more maxima of the scattered X-radiation, which have awidth of several degrees of the diffraction angle. However, particularlygood builder properties may even be achieved where the silicateparticles produce indistinct or even sharp diffraction maxima inelectron diffraction experiments. This can be interpreted to mean thatthe products have microcrystalline regions between 10 and a few hundrednm in size, values of up to at most 50 nm and especially up to at most20 nm being preferred. This type of X-ray amorphous silicate similarlypossesses a delayed dissolution in comparison with the customary waterglasses. Compacted/densified amorphous silicates, compounded amorphoussilicates and over dried X-ray amorphous silicates are particularlypreferred.

In the context of the present invention, the detergents and cleansingagents preferably comprise silicate(s), preferably alkali silicates,particularly preferably crystalline or amorphous alkali disilicates inquantities of 10 to 60 wt. %, preferably 15 to 50 wt. % and especially20 to 40 wt. %, each based on the weight of the detergent or cleansingagent.

When the silicates are incorporated as a component of dishwasherdetergents, then they preferably comprise at least one crystallinelayer-forming silicate of the general formula NaMSi_(x)O2_(x+1).yH₂O,wherein M represents sodium or hydrogen, x is a number from 1.9 to 22,preferably 1.9 to 4 and y stands for a number from 0 to 33. Thecrystalline layer-forming silicates of the formulaNaMSi_(x)O2_(2x+1).yH₂O are marketed for example by Clariant GmbH(Germany) under the trade names Na-SKS, eg. Na-SKS-1 (Na₂Si₂₂O₄₅.xH₂O,Kenyait), Na-SKS-2 (Na₂Si₁₄O₂₉.xH₂O, Magadiit), Na-SKS-3(Na₂Si₈O₁₇.xH₂O) or Na-SKS-4 (Na₂Si₄O₉.xH₂O, Makatit).

Crystalline, layered silicates of the above formula, in which x standsfor 2, are particularly suitable for the purposes of the presentinvention. Na-SKS-5 (α-Na₂Si₂O₅), Na-SKS-7 (β-Na₂Si₂O₅, Natrosilit),Na-SKS-9 (NaHSi₂O₅.H₂O), Na-SKS-10 (NaHSi₂O₅.3H₂O, Kanemit), Na-SKS-11(t-Na₂Si₂O₅) and Na-SKS-13 (NaHSi₂O₅) are most notably suitable,particularly, however, Na-SKS-6 (δ-Na₂Si₂O₅).

In the context of the present application, if silicates are incorporatedas components of dishwasher detergents, then these detergents comprise acontent by weight of crystalline layered silicates of formulaNaMSi_(x)O_(2x+1).yH₂O of 0.1 to 20 wt. %, preferably 0.2 to 15 wt. %and particularly 0.4 to 10 wt. %, each based on the total weight of theagent. Particularly preferred are especially those dishwasher detergentsthat have a total silicate content below 7 wt. %, advantageously below 6wt. %, preferably below 5 wt. %, particularly preferably below 4 wt. %,quite particularly preferably below 3 wt. % and especially below 2.5 wt.%, wherein this silicate, based on the total weight of the comprisedsilicate is advantageously at least 70 wt. %, preferably at least 80 wt.% and especially at least 90 wt. % of a silicate of the general formulaNaMSi_(x)O2_(x+1).yH₂O.

Of the suitable fine crystalline, synthetic zeolites containing boundwater, zeolite A and/or P are preferred. A particularly preferredzeolite P is zeolite MAP® (a commercial product of Crosfield). However,the zeolites X as well as mixtures of A, X and/or P are also suitable.Commercially available and preferred in the context of the presentinvention is, for example, also a co-crystallizate of zeolite X andzeolite A (ca. 80 wt. % zeolite X), which is marketed under the name ofVEGOBOND AX® by Condea Augusta S.p.A. and which can be described by theFormulanNa₂O.(1−n)K₂O.Al₂O₃.(2-2,5)SiO₂.(3.5-5.5)H₂OThe zeolite can be added both as the builder in a granular compound aswell as being used as a type of ‘powdering’ of the total mixture beingpressed, wherein normally, both ways are used to incorporate the zeolitein the premix. Suitable zeolites have a mean particle size of less than10 μm (volume distribution, as measured by the Coulter Counter Method)and comprise preferably 18 to 22% by weight and more preferably 20 to22% by weight of bound water.

Naturally, the generally known phosphates can also be added as builders,in so far that their use should not be avoided on ecological grounds.This is particularly true for the employment of the inventive agent asthe dishwasher detergent, as is particularly preferred in the context ofthe present application. In the detergent and cleansing agent industry,among the many commercially available phosphates, the alkali metalphosphates are the most important and pentasodium or pentapotassiumtriphosphates (sodium or potassium tripolyphosphate) are particularlypreferred.

“Alkali metal phosphates” is the collective term for the alkali metalsalts (more particularly sodium and potassium) of the various phosphoricacids that can be differentiated into metaphosphoric acids (HPO₃)_(n)and orthophosphoric acid (H₃PO₄) in addition to representatives ofhigher molecular weight. The phosphates combine several advantages: theyact as alkalinity sources, prevent lime deposits on machine parts andlime incrustations in fabrics and, in addition, contribute towards thecleansing power.

Exemplary suitable phosphates are sodium dihydrogen phosphate, NaH₂PO₄,in the form of the dihydrate (density 1.91 gcm⁻³ melting point 60°) orin the form of the monohydrate (density 2.04 gcm⁻³), disodium hydrogenphosphate (secondary sodium phosphate) Na₂HPO₄, that can be added inanhydrous form or with 2 mole (density 2.066 gcm⁻³, water loss at 95°C.), 7 mole (density 1.68 gcm³, melting point 48° C. losing 5H₂O) and 12mole water (density 1.52 gcm⁻³, melting point 35° C. losing 5. H₂O), inparticular, however, trisodium phosphate (tertiary sodium phosphate)Na₃PO₄, that can be added as the dodecahydrate, as the decahydrate(corresponding to 19-20% P₂O₅) and in anhydrous form (corresponding to39-40% P₂O₅).

A further preferred phosphate is tripotassium phosphate (tertiary ortribasic potassium phosphate), K₃PO₄. Further preferred are tetrasodiumdiphosphate (sodium pyrophosphate), Na₄P₂O₇, which exists in anhydrousform (density 2.534 gcm⁻³, melting point 988°, a figure of 880° has alsobeen mentioned) and as the decahydrate (density 1.815-1.836 gcm⁻³,melting point 94° with loss of water), as well as the correspondingpotassium salt potassium diphosphate (potassium pyrophosphate) K₄P₂O₇.

Relatively high molecular weight sodium and potassium phosphates areformed by condensation of NaH₂PO₄ or KH₂PO₄. They may be divided intocyclic types, namely the sodium and potassium metaphosphates, and chaintypes, the sodium and potassium polyphosphates. The chain types inparticular are known by various different names: fused or calcinedphosphates, Graham's salt, Kurrol's salt and Maddrell's salt. All highersodium and potassium phosphates are known collectively as condensedphosphates.

The industrially important pentasodium triphosphate, Na₅P₃O₁₀ (sodiumtripolyphosphate), is anhydrous or crystallizes with 6H₂O to anon-hygroscopic white water-soluble salt of the general formulaNaO—[P(O)(ONa)—O]_(n)—Na where n=3. The corresponding potassium saltpentapotassium triphosphate K₅P₃O₁₀ (potassium tripolyphosphate), iscommercialised, for example in the form of a 50 wt. % solution (>23%P₂O₅, 25% K₂O). The potassium polyphosphates are widely used in thedetergent industry. Sodium potassium tripolyphosphates also exist andare also usable in the scope of the present invention. They are formedfor example when sodium trimetaphosphate is hydrolyzed with KOH:(NaPO₃)₃+2 KOH→Na₃K₂P₃O₁₀+H₂O

According to the invention, they may be used in exactly the same way assodium tripolyphosphate, potassium tripolyphosphate or mixtures thereof.Mixtures of sodium tripolyphosphate and sodium potassiumtripolyphosphate or mixtures of potassium tripolyphosphate and sodiumpotassium tripolyphosphate or mixtures of sodium tripolyphosphate andpotassium tripolyphosphate and sodium potassium tripolyphosphate mayalso be used in accordance with the invention.

In the context of the present invention, if phosphates are incorporatedas the active detergent or cleansing substances in detergents orcleansing agents, then preferred agents comprise this/thesephosphate(s), preferably alkali metal phosphate(s), particularlypreferably pentasodium or pentapotassium triphosphate (sodium orpotassium triphosphate) in quantities of 5 to 80 wt. %, preferably 15 to75 wt. % and especially 20 to 70 wt. %, each based on the weight of thedetergent or cleansing agent.

It is particularly preferred to incorporate potassium tripolyphosphateand sodium tripolyphosphate in a proportion by weight of greater than1:1, preferably greater than 2:1, more preferably greater than 5:1,particularly preferably greater than 10:1 and especially greater than20:1. It is particularly preferred to incorporate exclusively potassiumtripolyphosphate without the addition of other phosphates.

Further builders are the alkalinity sources. Alkali metal hydroxides,alkali metal carbonates, alkali metal hydrogen carbonates, alkali metalsesquicarbonates, the cited alkali silicates, alkali metal silicates andmixtures of the cited materials are examples of alkalinity sources thatcan be used, the alkali carbonates being preferably used, especiallysodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate inthe context of this invention. A builder system comprising a mixture oftripolyphosphate and sodium carbonate is particularly preferred. Abuilder system comprising a mixture of tripolyphosphate and sodiumcarbonate and sodium disilicate is also particularly preferred. Becauseof their low chemical compatibility—in comparison with otherbuilders—with the usual ingredients of detergents and cleansing agents,the alkali metal hydroxides are preferably only incorporated in lowamounts, advantageously in amounts below 10 wt. %, preferably below 6wt. %, particularly preferably below 4 wt. % and particularly below 2wt. %, each based on the total weight of the detergent or cleansingagent. Agents that comprise less than 0.5 wt. %, based on the totalweight, and in particular no alkali metal hydroxide, are particularlypreferred.

Particularly preferred detergents and cleansing agents comprisecarbonate(s) and/or hydrogen carbonate(s), preferably alkalicarbonate(s), particularly preferably sodium carbonate in quantities of2 to 50 wt. %, preferably 5 to 40 wt. % and especially 7.5 to 30 wt. %,each based on the weight of the detergent or cleansing agent.Particularly preferred agents comprise, based on the weight of thedetergent or cleansing agent (i.e. the total weight of the combinationproduct without packaging), less than 20 wt. %, advantageously less than17 wt. %, preferably less than 13 wt. % and particularly less than 9 wt.% carbonate(s) and/or hydrogen carbonate(s), preferably alkalicarbonates, particularly preferably sodium carbonate.

Organic co builders include, in particular,polycarboxylates/polycarboxylic acids, polymeric polycarboxylates,aspartic acid, polyacetals, dextrins, other organic co builders (seebelow) and phosphonates. These classes of substances are describedbelow.

Useful organic builders are, for example, the polycarboxylic acidsusable in the form of their sodium salts, polycarboxylic acids in thiscontext being understood to be carboxylic acids that carry more than oneacid function. These include, for example, citric acid, adipic acid,succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid,fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid(NTA), providing its use is not ecologically unsafe, and mixturesthereof. Preferred salts are the salts of polycarboxylic acids such ascitric acid, adipic acid, succinic acid, glutaric acid, tartaric acid,sugar acids and mixtures thereof.

Acids per se can also be used. Besides their building effect, the acidsalso typically have the property of an acidifying component and, hencealso serve to establish a relatively low and mild pH in detergents andcleansing agents. Citric acid, succinic acid, glutaric acid, adipicacid, gluconic acid and any mixtures thereof are particularly mentionedin this regard.

Other suitable builders are additional polymeric polycarboxylates, forexample the alkali metal salts of polyacrylic or polymethacrylic acid,for example those with a relative molecular weight of 500 to 70 000g/mol.

The molecular weights mentioned in this specification for the polymericpolycarboxylates are weight-average molecular weights M_(w) of theparticular acid form which, fundamentally, were determined by gelpermeation chromatography (GPC), equipped with a UV detector. Themeasurement was carried out against an external polyacrylic acidstandard, which provides realistic molecular weight values by virtue ofits structural similarity to the polymers investigated. These valuesdiffer significantly from the molecular weights measured againstpolystyrene sulfonic acids as standard. The molecular weights measuredagainst polystyrene sulfonic acids are generally significantly higherthan the molecular weights mentioned in this specification.

Particularly suitable polymers are the polyacrylates, which preferablyhave a molecular weight of 2000 to 20 000 g/mol. By virtue of theirsuperior solubility, preferred representatives of this group are againthe short-chain polyacrylates, which have molecular weights of 2000 to10 000 g/mol and, more particularly, 3000 to 5000 g/mol.

Further suitable copolymeric polycarboxylates are particularly those ofacrylic acid with methacrylic acid and of acrylic acid or methacrylicacid with maleic acid. Copolymers of acrylic acid with maleic acid,which comprise 50 to 90 wt. % acrylic acid and 50 to 10 wt. % maleicacid, have proven to be particularly suitable. Their relative molecularweight, based on free acids, generally ranges from 2000 to 70 000 g/mol,preferably 20 000 to 50 000 g/mol and especially 30 000 to 40 000 g/mol.

The (co)polymeric polycarboxylates can be added either as powders or asaqueous solutions. The (co)polymeric polycarboxylate content of thedetergents or cleansing agents is preferably from 0.5 to 20% by weight,in particular from 3 to 10% by weight.

In order to improve the water solubility, the polymers can also compriseallylsulfonic acids as monomers, such as for example,allyloxybenzenesulfonic acid and methallylsulfonic acid

Particular preference is also given to biodegradable polymers comprisingmore than two different monomer units, examples being those comprising,as monomers, salts of acrylic acid and of maleic acid, and also vinylalcohol or vinyl alcohol derivatives, or those comprising, as monomers,salts of acrylic acid and of 2-alkylallylsulfonic acid, and also sugarderivatives.

Other preferred copolymers are those, which preferably contain acroleinand acrylic acid/acrylic acid salts or acrolein and vinyl acetate asmonomers.

Similarly, other preferred builders are polymeric aminodicarboxylicacids, salts or precursors thereof. Polyaspartic acids or their saltsare particularly preferred.

Further preferred builders are polyacetals that can be obtained bytreating dialdehydes with polyol carboxylic acids that possess 5 to 7carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals areobtained from dialdehydes like glyoxal, glutaraldehyde,terephthalaldehyde as well as their mixtures and from polycarboxylicacids like gluconic acid and/or glucoheptonic acid.

Further suitable organic builders are dextrins, for example oligomers orpolymers of carbohydrates that can be obtained by the partial hydrolysisof starches. The hydrolysis can be carried out using typical processes,for example acidic or enzymatic catalyzed processes. The hydrolysisproducts preferably have average molecular weights in the range 400 to500 000 g/mol. A polysaccharide with a dextrose equivalent (DE) of 0.5to 40 and, more particularly, 2 to 30 is preferred, the DE being anaccepted measure of the reducing effect of a polysaccharide incomparison with dextrose, which has a DE of 100. Both maltodextrins witha DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37and also so-called yellow dextrins and white dextrins with relativelyhigh molecular weights of 2000 to 30 000 g/mol may be used.

The oxidized derivatives of such dextrins concern their reactionproducts with oxidizing agents that are capable of oxidizing at leastone alcohol function of the saccharide ring to the carboxylic acidfunction.

Oxydisuccinates and other derivatives of disuccinates, preferablyethylenediamine disuccinate are also further suitable cobuilders.Ethylenediamine-N,N′-disuccinate (EDDS) is preferably used here in theform of its sodium or magnesium salts. In this context, glycerindisuccinates and glycerin trisuccinates are also preferred. Suitableaddition quantities in zeolite-containing and/or silicate-containingformulations range from 3 to 15% by weight.

Other useful organic co-builders are, for example, acetylatedhydroxycarboxylic acids and salts thereof which optionally may also bepresent in lactone form and which contain at least 4 carbon atoms, atleast one hydroxyl group and at most two acid groups.

The phosphonates represent a further class of substances with cobuilderproperties. In particular, they are hydroxyalkane phosphonates oraminoalkane phosphonates. Among the hydroxyalkane phosphonates,1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance asthe cobuilder. It is normally added as the sodium salt, the disodiumsalt reacting neutral and the tetrasodium salt reacting alkaline (pH 9).Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologs arepreferably chosen as aminoalkane phosphonates. They are preferably addedin the form of the neutral-reacting sodium salts, e.g. as the hexasodiumsalt of EDTMP or as the hepta and octasodium salt of DTPMP. Of thephosphonates, HEDP is preferably used as the builder. The aminoalkanephosphonates additionally possess a pronounced ability to complex heavymetals. Accordingly, it can be preferred, particularly where the agentsalso contain bleach, to use aminoalkane phosphonates, particularlyDTPMP, or mixtures of the mentioned phosphonates.

In addition, any compounds capable of forming complexes with alkalineearth metal ions may be used as co-builders.

In the scope of the present application, particularly preferreddishwasher detergents according to the invention comprise 10 to 80 wt.%, preferably 15 to 75 wt. %, particularly preferably 20 to 70 wt. % andparticularly 25 to 65 wt. % of one or more water-soluble builders.

Surfactants

In addition to the non-ionic surfactants described above, the group ofsurfactants also includes the anionic, cationic and amphotericsurfactants.

Exemplary suitable anionic surfactants are those of the sulfonate andsulfate type. Suitable surfactants of the sulfonate type areadvantageously C₉₋₁₃-alkylbenzene sulfonates, olefin sulfonates, i.e.mixtures of alkene- and hydroxyalkane sulfonates, and disulfonates, asare obtained, for example, from C₁₂₋₁₈-monoolefins having a terminal orinternal double bond, by sulfonation with gaseous sulfur trioxide andsubsequent alkaline or acidic hydrolysis of the sulfonation products.Those alkane sulfonates, obtained from C₁₂₋₁₈ alkanes bysulfochlorination or sulfoxidation, for example, with subsequenthydrolysis or neutralization, are also suitable. The esters ofα-sulfofatty acids (ester sulfonates), e.g. the α-sulfonated methylesters of hydrogenated coco-, palm nut- or tallow acid are likewisesuitable.

Further suitable anionic surfactants are sulfated fatty acid esters ofglycerine. They include the mono-, di- and triesters and also mixturesof them, such as those obtained by the esterification of a monoglycerinwith 1 to 3 moles fatty acid or the transesterification of triglycerideswith 0.3 to 2 moles glycerin. Preferred sulfated fatty acid esters ofglycerol in this case are the sulfated products of saturated fatty acidswith 6 to 22 carbon atoms, for example caproic acid, caprylic acid,capric acid, myristic acid, lauric acid, palmitic acid, stearic acid orbehenic acid.

Preferred alk(en)yl sulfates are the alkali and especially sodium saltsof the sulfuric acid half-esters derived from the C₁₂-C₁₈ fattyalcohols, for example from coconut butter alcohol, tallow alcohol,lauryl, myristyl, cetyl or stearyl alcohol or from C₁₀-C₂₀ oxo alcoholsand those half-esters of secondary alcohols of these chain lengths.Additionally preferred are alk(en)yl sulfates of the said chain lengths,which contain a synthetic, straight-chained alkyl group produced on apetro-chemical basis, which show similar degradation behaviour to thesuitable compounds based on fat chemical raw materials. TheC₁₂-C₁₆-alkyl sulfates and C₁₂-C₁₅-alkyl sulfates and C₁₄-C₁₅ alkylsulfates are preferred on the grounds of laundry performance. 2,3 alkylsulfates, which can be obtained from Shell Oil Company under the tradename DAN®, are also suitable anionic surfactants.

Sulfuric acid mono-esters derived from straight-chained or branchedC₇₋₂₁ alcohols ethoxylated with 1 to 6 moles ethylene oxide are alsosuitable, for example 2-methyl-branched C₉₋₁₁ alcohols with an averageof 3.5 mol ethylene oxide (EO) or C₁₂₋₁₈ fatty alcohols with 1 to 4 EO.Due to their high foaming performance, they are only used in fairlysmall quantities in cleansing agents, for example in amounts of 1 to 5%by weight.

Other suitable anionic surfactants are the salts of alkylsulfosuccinicacid, which are also referred to as sulfosuccinates or esters ofsulfosuccinic acid and the monoesters and/or di-esters of sulfosuccinicacid with alcohols, preferably fatty alcohols and especially ethoxylatedfatty alcohols. Preferred sulfosuccinates contain C₈₋₁₈ fatty alcoholgroups or mixtures of them. Especially preferred sulfosuccinates containa fatty alcohol residue derived from the ethoxylated fatty alcohols thatare under consideration as non-ionic surfactants (see descriptionbelow). Once again the especially preferred sulfosuccinates are those,whose fatty alcohol residues are derived from ethoxylated fatty alcoholswith narrow range distribution. It is also possible to usealk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in thealk(en)yl chain, or salts thereof.

Soaps in particular can be considered as further anionic surfactants.Saturated fatty acid soaps are suitable, such as the salts of lauricacid, myristic acid, palmitic acid, stearic acid, hydrogenated erucicacid and behenic acid, and especially soap mixtures derived from naturalfatty acids such as coconut oil fatty acid, palm kernel oil fatty acidor tallow fatty acid.

Anionic surfactants, including soaps may be in the form of their sodium,potassium or ammonium salts or as soluble salts of organic bases, suchas mono-, di- or triethanolamine. Preferably, anionic surfactants are inthe form of their sodium or potassium salts, especially sodium.

When the anionic surfactants are components of dishwasher detergents,their content, based on the total weight of the agent, is advantageouslyless than 4% by weight, preferably less than 2% by weight and quiteparticularly preferably less than 1% by weight. Dishwasher detergents,which comprise no anionic surfactants, are particularly preferred.

Cationic and/or amphoteric surfactants can be added instead of, or incombination with the cited surfactants.

As the cationic active substances, cationic compounds of the followingthree Formulae IX, X or XI can be incorporated for example:

in which each group R¹, independently of one another, is chosen fromC₁₋₆-alkyl, -alkenyl or -hydroxyalkyl groups; each group R²,independently of one another, is chosen from C₈₋₂₈-alkyl or -alkenylgroups; R³═R¹ or (CH₂)_(n)—T—R²; R⁴═R¹ or R² or (CH₂)_(n)—T—R²; T=—CH₂—,—O—CO— or —CO—O— and n is an integer from 0 to 5.

In dishwasher detergents, the content of cationic and/or amphotericsurfactants is advantageously less than 6% by weight, preferably lessthan 4% by weight, quite particularly preferably less than 2% by weightand in particular less than 1% by weight. Dishwasher detergents, whichcomprise no cationic or amphoteric surfactants, are particularlypreferred.

Polymers

The group of polymers includes, in particular the active detergentpolymers or active cleansing polymers, for example, the rinsing polymersand/or polymers active for water softening. Generally, in addition tonon-ionic polymers, cationic, anionic or amphoteric polymers aresuitable for incorporation in detergents or cleansing agents.

Exemplary polymers active for water softening are polymers with sulfonicacid groups, which are especially preferably added.

Particularly preferred suitable polymers comprising sulfonic acid groupsare copolymers of unsaturated carboxylic acids, monomers comprisingsulfonic acid groups and optional further ionic or non-ionogenicmonomers.

In the context of the present invention, unsaturated carboxylic acids ofFormula XII are preferred monomers,R¹(R²)C═C(R³)COOH  (XII),in which R¹ to R³ independently of one another stands for —H, —CH₃, alinear or branched, saturated alkyl group containing 2 to 12 carbonatoms, a linear or branched, mono- or polyunsaturated alkenyl groupcontaining 2 to 12 carbon atoms, with —NH₂, —OH or —COOH substitutedalkyl or alkenyl groups as defined above or —COOH or —COOR⁴, where R⁴ isa saturated or unsaturated, linear or branched hydrocarbon groupcontaining 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids corresponding to Formula XII,acrylic acid (R¹═R²═R³═H), methacrylic acid (R¹═R²═H; R³═CH₃) and/ormaleic acid (R¹═COOH; R²═R³═H) are particularly preferred.

The preferred monomers containing sulfonic acid groups correspond tothose of the Formula XIII,R⁵(R⁶)C═C(R⁷)—X—SO₃H  (XIII),in which R⁵ to R⁷ independently of one another stand for —H, —CH₃, alinear or branched, saturated alkyl group containing 2 to 12 carbonatoms, a linear or branched, mono- or polyunsaturated alkenyl groupcontaining 2 to 12 carbon atoms, with —NH₂, —OH or —COOH substitutedalkyl or alkenyl groups as defined above or —COOH or —COOR⁴, where R⁴ isa saturated or unsaturated, linear or branched hydrocarbon groupcontaining 1 to 12 carbon atoms, and X is an optionally present spacergroup selected from —(CH₂)_(n)— with n=0 to 4, —COO—(CH₂)_(k)— with k=1to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—.

Among these monomers, those corresponding to Formulae XIIIa, XIIIband/or XIIIc are preferred,H₂C═CH—X—SO₃H  (XIIIa),H₂C═C(CH₃)—X—SO₃H  (XIIIb),HO₃S—X—(R⁶)C═C(R⁷)—X—SO₃H  (XIIIc),in which R⁶ und R⁷ independently of one another are selected from —H,—CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂ and X is an optionally presentspacer group selected from —(CH₂)_(n)— with n=0 to 4, —COO—(CH₂)_(k)—with k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—.

Particularly preferred monomers containing sulfonic acid groups are1-acrylamido-1-propanesulfonic acid (X=—C(O)NH—CH(CH₂CH₃) in formulaXIa), 2-acrylamido-2-propanesulfonic acid (X=—C(O)NH—C(CH₃)₂ in formulaXIIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid(X=—C(O)NH—CH(CH₃)CH₂— in formula XIIIa),2-methacrylamido-2-methyl-1-propanesulfonic acid (X=—C(O)NH—CH(CH₃)CH₂—in formula XIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid(X=—C(O)NH—CH₂CH(OH)CH₂— in formula XIIIb), allyl sulfonic acid (X═CH₂in formula XIIIa), methallylsulfonic acid (X═CH₂ in formula XIIIb),allyloxybenzenesulfonic acid (X=—CH₂—O—C₆H₄— in formula XIIIa),methallyloxybenzenesulfonic acid (X=—CH₂—O—C₆H₄— in formula XIIIb),2-hydroxy-3-(2-propenyloxy)-propanesulfonic acid,2-methyl-2-propene-1-sulfonic acid (X═CH₂ in formula XIIIb),styrenesulfonic acid (X═C₆H₄ in formula XIIIa), vinylsulfonic acid (Xnot present in formula XIIIa), 3-sulfopropyl acrylate(X=—C(O)NH—CH₂CH₂CH₂— in formula XIIIa), 3-sulfopropyl methacrylate(X=—C(O)NH—CH₂CH₂CH₂— in formula XIIIb), sulfomethacrylamide (X=—C(O)NH—in formula XIIIb), sulfomethylmethacrylamide (X=—C(O)NH—CH₂— in formulaXIIIb) and water-soluble salts of the acids mentioned.

Additional ionic or non-ionogenic monomers are particularlyethylenically unsaturated compounds. The polymers used in accordancewith the invention preferably contain less than 20% by weight, based onpolymer, of monomers belonging to group iii). Particularly preferredpolymers for use consist solely of monomers belonging to groups i) andii).

In summary copolymers of

i) unsaturated carboxylic acids of Formula XIIR¹(R²)C═C(R³)COOH  (XII),in which R¹ to R³ independently of one another stands for —H, —CH₃, alinear or branched, saturated alkyl group containing 2 to 12 carbonatoms, a linear or branched, mono- or polyunsaturated alkenyl groupcontaining 2 to 12 carbon atoms, with —NH₂, —OH or —COOH substitutedalkyl or alkenyl groups as defined above or —COOH or —COOR⁴, where R⁴ isa saturated or unsaturated, linear or branched hydrocarbon groupcontaining 1 to 12 carbon atoms,ii) monomers containing sulfonic acid groups corresponding to FormulaXIIIR⁵(R⁶)C═C(R⁷)—X—SO₃H  (XIII),in which R⁵ to R⁷ independently of one another stands for —H, —CH₃, alinear or branched, saturated alkyl group containing 2 to 12 carbonatoms, a linear or branched, mono- or polyunsaturated alkenyl groupcontaining 2 to 12 carbon atoms, with —NH₂, —OH or —COOH substitutedalkyl or alkenyl groups as defined above or —COOH or —COOR⁴, where R⁴ isa saturated or unsaturated, linear or branched hydrocarbon groupcontaining 1 to 12 carbon atoms and X stands for an optionally presentspacer group, selected from —(CH₂)_(n)— with n=0 to 4, —COO—(CH₂)_(k)—with k=1 to 6, —C(O)—NH—C(CH₃)₂— and —C(O)—NH—CH(CH₂CH₃)—iii) optional additional ionic or non-ionic monomers are particularlypreferred.

Further particularly preferred copolymers consist of

-   -   i) one or a plurality of unsaturated carboxylic acids from the        group acrylic acid, methacrylic acid and/or maleic acid    -   ii) one or a plurality of monomers containing sulfonic acid        groups corresponding to Formulae XIIIa, XIIIb and/or XIIIc:        H₂C═CH—X—SO₃H  (XIIIa),        H₂C═C(CH₃)—X—SO₃H  (XIIIb),        HO₃S—X—(R⁶)C═C(R⁷)—X—SO₃H  (XIIIc),        in which R⁶ and R⁷ independently of one another are selected        from —H, —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂ and X is an        optionally present spacer group selected from —(CH₂)_(n)— with        n=0 to 4, —COO—(CH₂)_(k)— with k=1 to 6, —C(O)—NH—C(CH₃)₂— and        —C(O)—NH—CH(CH₂CH₃)—    -   iii) optional additional ionic or non-ionic monomers.

The copolymers can contain monomers from groups (i) and (ii) andoptionally (iii) in varying amounts, wherein all representatives ofgroup (i) can be combined with all representatives of group (ii) and allrepresentatives of group (iii). Particularly preferred polymers havedefined structural units, which are described below.

For example, copolymers are preferred, which comprise structural unitsof Formula XIV—[CH₂—CHCOOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)—  (XIV),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are preferred.

These polymers are produced by copolymerization of acrylic acid with anacrylic acid derivative containing sulfonic acid groups. If the acrylicacid derivative containing sulfonic acid groups is copolymerized withmethacrylic acid, then another polymer results whose incorporation islikewise preferred. The appropriate copolymers comprise structural unitsof Formula XV—[CH₂—C(C H₃)COOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)—  (XV),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are preferred.

Entirely analogously, acrylic acid and/or methacrylic acid may also becopolymerized with methacrylic acid derivatives containing sulfonic acidgroups, so that the structural units in the molecule are changed.Consequently, copolymers that comprise structural units of Formula XVI—[CH₂—CHCOOH]_(m)—[CH₂—C(CH₃)C(O)—Y—SO₃H]_(p)—  (XVI),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are also preferred as copolymers that have structuralunits of Formula XVII.—[CH₂—C(CH₃)COOH]_(m)—[CH₂—C(CH₃)C(O)—Y—SO₃H]_(p)—  (XVII),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)—.

Instead of acrylic acid and/or methacrylic acid or in addition to them,maleic acid can also be incorporated as the particularly preferredmonomer from group i). In this way, one arrives at inventively preferredcopolymers that comprise structural units of the Formula XVIII—[HOOCCH—CHCOOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)—  (XVIII),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are preferred, and to inventively preferred copolymersthat comprise structural units corresponding to Formula XIX—[HOOCCH—CHCOOH]_(m)—[CH₂—C(CH₃)C(O)O—Y—SO₃H]_(p)—  (XIX),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are preferred.

In summary, preferred copolymers according to the invention comprisestructural units of Formula XIV and/or XV and/or XVI and/or XVII and/orXVIII and/or XIX —[CH₂—CHCOOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)— (XIV),—[CH₂—C(CH₃)COOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)— (XV),—[CH₂—CHCOOH]_(m)—[CH₂—C(CH₃)C(O)—Y—SO₃H]_(p)— (XVI),—[CH₂—C(CH₃)COOH]_(m)—[CH₂—C(CH₃)C(O)—Y—SO₃H]_(p)— (XVII),—[HOOCCH—CHCOOH]_(m)—[CH₂—CHC(O)—Y—SO₃H]_(p)— (XVIII),—[HOOCCH—CHCOOH]_(m)—[CH₂—C(CH₃)C(O)O—Y—SO₃H]_(p)— (XIX),in which m and p each stand for a whole natural number between 1 and2000 and Y stands for a spacer group selected from substituted orunsubstituted aliphatic, aromatic or araliphatic hydrocarbon groupscontaining 1 to 24 carbon atoms, wherein spacer groups, in which Yrepresents —O—(CH₂)_(n)— with n=0 to 4, —O—(C₆H₄)—, —NH—C(CH₃)₂— or—NH—CH(CH₂CH₃)— are preferred.

The sulfonic acid groups may be present in the polymers completely orpartly in neutralized form, i.e. the acidic hydrogen atom of thesulfonic acid groups can be replaced by metal ions, preferably alkalimetal ions and more particularly sodium ions, in some or all of thesulfonic acid groups. The addition of copolymers containing partly orfully neutralized sulfonic acid groups is preferred according to theinvention.

The monomer distribution of the inventively preferred copolymers usedranges for copolymers that comprise only monomers defined in groups (i)and (ii) from preferably 5 to 95 wt. % (i) and (ii) respectively,particularly preferably 50 to 90 wt. % monomer from group (i) and 10 to50 wt. % monomer from group (ii) respectively, based on the polymer.

Particularly preferred terpolymers are those that comprise 20 to 85 wt.% monomer from group (i), 10 to 60 wt. % monomer from group (ii) and 5to 30 wt. % monomer from group (iii).

The molecular weight of the inventively preferred sulfo-copolymers usedcan be varied to adapt the properties of the polymer to the desiredapplication requirement. Preferred detergents or cleansing agentcompositions are characterized in that the molecular weights of thecopolymers are 2000 to 200 000 gmol⁻¹, preferably 4000 to 25 000 gmol⁻¹and especially 5000 to 15 000 gmol⁻¹.

Bleaching Agents

The detergents or cleansing agents can comprise bleach activators inorder to achieve an improved bleaching action on washing or cleaning attemperatures of 60° C. and below. Bleach activators, which can be usedare compounds which, under perhydrolysis conditions, yield aliphaticperoxycarboxylic acids having preferably 1 to 10 carbon atoms, inparticular 2 to 4 carbon atoms, and/or optionally substituted perbenzoicacid. Substances, which carry O-acyl and/or N-acyl groups of said numberof carbon atoms and/or optionally substituted benzoyl groups, aresuitable. Preference is given to polyacylated alkylenediamines, inparticular tetraacetyl ethylenediamine (TAED), acylated triazinederivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylatedglycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides,in particular N-nonanoyl succinimide (NOSI), acylated phenol sulfonates,in particular n-nonanoyl- or isononanoyloxybenzene sulfonate (n- oriso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride,acylated polyhydric alcohols, in particular triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In the context of the present application, further preferred addedbleach activators are compounds from the group of cationic nitriles,particularly cationic nitriles of the Formula

in which R¹ stands for —H, —CH₃, a C₂₋₂₄ alkyl or alkenyl group, asubstituted C₂₋₂₄ alkyl or alkenyl group having at least one substituentfrom the group of —Cl, —Br, —OH, —NH₂, —CN, an alkyl or alkenylarylgroup having a C₁₋₂₄ alkyl group or for a substituted alkyl oralkenylaryl group having a C₁₋₂₄ alkyl group and at least a furthersubstituent on the aromatic ring, R² and R³, independently of oneanother are selected from —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃,—CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH,—CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, —(CH₂CH₂—O)_(n)H with n=1, 2, 3, 4, 5or 6 and X is an anion.

Particularly preferably, a cationic nitrile of the formula

is particularly preferred, in which R⁴, R⁵ and R⁶ independently of oneanother are selected from —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃,wherein R⁴ can also be —H and X is an anion, wherein preferablyR⁵═R⁵=—CH₃ and in particular R⁴═R⁵═R⁵=—CH₃ and compounds of the formulae(CH₃)₃N⁽⁺⁾CH₂—CN X⁻, (CH₃CH₂)₃N⁽⁺⁾CH₂—CN X⁻, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂—CN X⁻,(CH₃CH(CH₃))₃N⁽⁺⁾CH₂—CN X⁻, or (HO—CH₂—CH₂)₃N⁽⁺⁾CH₂—CN X⁻ areparticularly preferred, wherein once again the cationic nitrile of theformula (CH₃)₃N⁽⁺⁾CH₂—CN X⁻, in which X⁻ stands for an anion selectedfrom the group chloride, bromide, iodide, hydrogen sulfate,methosulfate, p-toluene sulfonate (tosylate) or xylene sulfonate.

Bleach activators, which can be used are compounds which, underperhydrolysis conditions, yield aliphatic peroxycarboxylic acids havingpreferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms,and/or optionally substituted perbenzoic acid. Substances, which carryO-acyl and/or N-acyl groups of said number of carbon atoms and/oroptionally substituted benzoyl groups, are suitable. Preference is givento polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylatedglycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides,in particular N-nonanoyl succinimide (NOSI), acylated phenol sulfonates,in particular n-nonanoyl- or isononanoyloxybenzene sulfonate (n- oriso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride,acylated polyhydric alcohols, in particular triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran,N-methyl-morpholinium-acetonitrile-ethyl sulfate (MMA) as well asacetylated sorbitol and mannitol or their mixtures (SORMAN), acylatedsugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetyl xylose and octaacetyl lactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone, and/orN-acylated lactams, for example N-benzoyl caprolactam. Hydrophillicallysubstituted acyl acetals and acyl lactams are also preferably used.Combinations of conventional bleach activators may also be used.

In addition to, or instead of the conventional bleach activatorsmentioned above, so-called bleach catalysts may also be incorporated.These substances are bleach-boosting transition metal salts ortransition metal complexes such as, for example, manganese-, iron-,cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium andcopper complexes with nitrogen-containing tripod ligands, as well ascobalt-, iron-, copper- and ruthenium-ammine complexes may also beemployed as the bleach catalysts.

When additional bleach activators are intended to be used in addition tothe nitrilequats, preferred bleach activators are added from the groupof polyacylated alkylenediamines, more particularly tetraacetylethylenediamine (TAED), N-acyl imides, more particularly N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularlyn-nonanoyl- or isononanoyl-oxybenzene sulfonate (n- or iso-NOBS),N-methyl morpholinium acetonitrile methyl sulfate (MMA), preferably inquantities of up to 10% by weight, more preferably in quantities of 0.1%by weight to 8% by weight, especially 2 to 8% by weight and especiallypreferably 2 to 6% by weight, based on the total weight of the bleachactivator-containing agent.

Bleach-boosting transition metal complexes, more particularly containingthe central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferablyselected from the group of manganese and/or cobalt salts and/orcomplexes, particularly preferably the cobalt (ammine) complexes, cobalt(acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt ormanganese and manganese sulfate, are also used in typical quantities,preferably in a quantity of up to 5% by weight, especially in a quantityof 0.0025% by weight to 1% by weight and particularly preferably in aquantity of 0.01% by weight to 0.25% by weight, based on the totalweight of the bleach activator-containing agent. In special cases,however, even more bleach activator may be used.

Glass Corrosion Inhibitors

Glass corrosion inhibitors prevent the occurrence of smears, streaks andscratches as well as iridescence on the glass surface of glasses washedin an automatic dishwasher. Preferred glass corrosion inhibitors comefrom the group of magnesium and/or zinc salts and/or magnesium and/orzinc complexes.

A preferred class of compounds that can be used to prevent glasscorrosion are insoluble zinc salts.

In terms of the preferred embodiment, insoluble zinc salts are zincsalts with a solubility of maximum 10 grams zinc salt per liter of waterat 20° C. According to the invention, examples of particularly preferredinsoluble zinc salts are zinc silicate, zinc carbonate, zinc oxide,basic zinc carbonate (Zn₂(OH)₂CO₃), zinc hydroxide, zinc oxalate, zincmonophosphate (Zn₃(PO₄)₂), and zinc pyrophosphate (Zn₂(P₂O₇)).

The cited zinc compounds are preferably used in quantities that producean amount of zinc ions in the agent between 0.02 and 10 wt. %,preferably between 0.1 and 5.0 wt. % and especially between 0.2 and 1.0wt. %, based on the total agent containing the glass corrosioninhibitor. The exact content of the zinc salt or zinc salts in the agentnaturally depends on the type of zinc salt—the lower the solubility ofthe added zinc salt, the higher must be its concentration in the agents.

As for the most part the insoluble zinc salts remain unchanged duringthe dishwasher process, the particle size of the salts is an importantcriteria for the salts not to stick to the glassware or machine parts.Agents are preferred in which the insoluble zinc salts have a particlesize below 1.7 mm.

When the maximum particle size of the insoluble zinc salt lies below 1.7mm, one need not worry about insoluble residues in the dishwasher.Preferably, in order to further minimise the danger of insolubleresidues, the insoluble zinc salt has an average particle size that liesmarkedly below this value, for example an average particle size of lessthan 250 μm. This is more and more true as the solubility of the zincsalt decreases. In addition, the efficiency of the glass corrosioninhibition increases with decreasing particle size. For zinc salts withvery low solubility, the particle size preferably lies below 100 μm. Forzinc salts with even lower solubility, it can be even less; for examplethe average particle size for the very poorly soluble zinc oxidepreferably lies below 100 μm.

A further preferred class of compounds are magnesium and/or zinc salt(s)of at least one monomeric and/or polymeric organic acid. These ensurethat even on repeated use, the surfaces of the glassware are notcorroded, especially that no smears, streaks and scratches oriridescence occur on the glass surfaces.

Although any magnesium and/or zinc salt(s) of monomeric and/or polymericorganic acids can be used, the magnesium and/or zinc salt(s) ofmonomeric and/or polymeric organic acids from the groups of thenon-branched, saturated or unsaturated monocarboxylic acids, thebranched, saturated or unsaturated monocarboxylic acids, the saturatedand unsaturated dicarboxylic acids, the aromatic mono-, di- andtricarboxylic acids, the sugar acids, the hydroxy acids, the oxoacids,the amino acids and/or the polymeric carboxylic acids.

The spectrum of the inventive preferred zinc salts of organic acids,preferably organic carboxylic acids, ranges from salts that aredifficulty soluble or insoluble in water, i.e. with a solubility below100 mg/L, preferably below 10 mg/L, or especially are insoluble, to suchsalts with solubilities in water greater than 100 mg/L, preferably over500 mg/L, particularly preferably over 1 g/L and especially over 5 g/L(all solubilities at a water temperature of 20° C.). The first group ofzinc salts includes zinc citrate, zinc oleate and zinc stearate, thegroup of soluble zinc salts includes for example, zinc formate, zincacetate, zinc lactate und zinc gluconate.

A particular advantageous glass corrosion inhibitor is a zinc salt of anorganic carboxylic acid, particularly preferably a zinc salt from thegroup zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinclactate and/or zinc citrate. Zinc ricinoleate, zinc abietate and zincoxalate are also preferred.

In the context of the present invention, the content of zinc salt in thecleansing agent is advantageously between 0.1 and 5 wt. %, preferablybetween 0.2 and 4.0 wt. % and especially between 0.4 and 3 wt. %, andthe content of zinc in the oxidized form (calculated as Zn²⁺) between0.01 and 1 wt. %, preferably between 0.02 and 0.5 wt. % and especiallybetween 0.04 and 0.2 wt. % respectively, based on the total weight ofthe agent containing the glass corrosion inhibitor.

Corrosion Inhibitors

Corrosion inhibitors serve to protect the tableware or the machine,silver protection agents being particularly important in automaticdishwashing. Substances known from the prior art can be incorporated.Above all, silver protectors selected from the group of triazoles,benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazolesand the transition metal salts or complexes may generally be used.Benzotriazole and/or alkylaminotriazole are particularly preferablyused. Exemplary inventively preferred suitable3-amino-5-alkyl-1,2,4-triazoles can be cited: 5-propyl-, -butyl-,-pentyl-, -heptyl-, -octyl-, -nonyl-, -decyl-, -undecyl-, -dodecyl-,-isononyl-, -versatic-10-acidalkyl-, -phenyl-, -p-tolyl-, -(4-tert.butylphenyl)-, -(4-methoxyphenyl)-, -(2-, -3-, -4-pyridyl)-,-(2-thienyl)-, -(5-methyl-2-furyl)-, -(5-oxo-2-pyrrolidinyl)-,-3-amino-1,2,4-triazole. In dishwasher detergents, thealkylamino-1,2,4-triazoles or their physiologically compatible salts areused in a concentration of 0.001 to 10 wt. %, preferably 0.0025 to 2 wt.%, particularly preferably 0.01 to 0.04 wt. %. Preferred acids for thesalt formation are hydrochloric acid, sulfuric acid, phosphoric acid,carbonic acid, sulfurous acid, organic carboxylic acids like aceticacid, glycolic acid, citric acid, succinic acid. Quite particularlyactive are 5-pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-,5-versatic-10-acidalkyl-3-amino-1,2,4-triazoles as well as mixtures ofthese substances.

Frequently encountered in cleansing formulations, furthermore, areagents containing active chlorine, which may significantly reducecorrosion of the silver surface. In chlorine-free cleansing products,particular use is made of oxygen-containing and nitrogen-containingorganic redox-active compounds, such as dihydric and trihydric phenols,e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid,phloroglucinol, pyrogallol and derivatives of these classes of compound.Salts and complexes of inorganic compounds, such as salts of the metalsMn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Preference isgiven in this context to the transition metal salts selected from thegroup consisting of manganese and/or cobalt salts and/or complexes,particularly preferably cobalt ammine complexes, cobalt acetatocomplexes, cobalt carbonyl complexes, the chlorides of cobalt or ofmanganese, and manganese sulfate. Zinc compounds may also be used toprevent corrosion of tableware.

Redox-active substances may be added instead of, or in addition to theabove described silver protection agents, e.g. the benzotriazoles. Thesesubstances are preferably inorganic redox-active substances from thegroup of salts and/or complexes of manganese, titanium, zirconium,hafnium, vanadium, cobalt or cerium, in which the cited metals exist inthe valence states II, III, IV, V or VI.

The metal salts or complexes used should be at least partially solublein water. Suitable counterions for the salt formation include all usualmono, di or trivalent negatively charged inorganic anions, e.g. oxide,sulfate, nitrate, fluoride and also organic anions e.g. stearate. In thecontext of the invention, metal complexes are compounds that consist ofa central atom and one or several ligands as well as optionally one orseveral of the abovementioned anions in addition. The central atom isone of the abovementioned metals in one of the abovementioned valencestates. Ligands are neutral molecules or anions, which are monodentateor bidentate; in the context of the invention, the term “ligands” isdiscussed in more detail in “Römpp Chemie Lexikon, Georg Thieme VerlagStuttgart/New York, 9. Edition, 1990, page 2507”. If the charge on thecentral atom and the charge of the ligand(s) do not add up to zero, thenaccording to whether a cationic or an anionic residual charge ispresent, either one or several of the abovementioned anions or one ormore of the cations e.g. sodium, potassium, ammonium ions equalise thecharge difference. Suitable complex builders are e.g. citrate,acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The current definition for “valence state” in chemistry is given in“Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9.Edition, 1991, page 3168”.

Particularly preferred metal salts and/or metal complexes are selectedfrom the group MnSO4, Mn(II) citrate, Mn(II) stearate, Mn(II)acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄,VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃ as well as theirmixtures, such that preferred inventive automatic dishwasher agents arecharacterized in that the metal salts and/or metal complexes areselected from the group MnSO₄, Mn(II) citrate, Mn(II) stearate, Mn(II)acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄,VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃.

These metal salts and/or metal complexes are generally commerciallyavailable substances that can be added in the inventive agents forsilver corrosion protection without prior cleaning. The mixture ofpentavalent and tetravalent vanadium (V₂O₅, VO₂, V₂O₄), known from theSO₃ manufacturing process (Contact Process) is suitable, for example,similarly titanyl sulfate, TiOSO₄ that is formed by diluting a solutionof Ti(SO₄)₂.

The inorganic redox-active substances, particularly metal salts or metalcomplexes are preferably coated, i.e. completely coated with awater-impermeable material that is easily soluble at the cleaningtemperature, so as to prevent any premature decomposition or oxidationon storage. Preferred coating materials, which are applied using knownprocesses, for instance hot melt coating process from Sandwik in thefood industry, are paraffins, microwaxes, waxes of natural origin suchas candelilla wax, carnuba wax, beeswax, higher-melting alcohols such asfor example hexadecanol, soaps or fatty acids. The coating material,which is solid at room temperature, is applied in the molten state ontothe material to be coated, e.g. by projecting a continuous stream offinely-divided material to be coated through a likewise continuouslyproduced atomized spray zone of molten coating material. The meltingpoint must be chosen such that the coating material easily dissolvesduring the silver treatment and quickly solidifies. The melting pointshould ideally lie in the range 45° C. and 65° C. and preferably in therange 50° C. to 60° C.

The cited metal salts and/or metal complexes are comprised in thecleansing agents, preferably in a quantity of 0.05 to 6 wt. %,preferably 0.2 to 2.5 wt. %, each based on the total weight of the agentcontaining the corrosion inhibitor.

Enzymes

Enzymes can be incorporated to increase the washing or cleansingperformance of detergents or cleansing agents. These particularlyinclude proteases, amylases, lipases, hemicellulases, cellulases oroxidoreductases as well as preferably their mixtures. In principle,these enzymes are of natural origin; improved variants based on thenatural molecules are available for use in detergents and accordinglythey are preferred. The agents according to the invention preferablycomprise enzymes in total quantities of 1×10⁻⁶ to 5 weight percent basedon active protein. The protein concentration can be determined usingknown methods, for example the BCA Process or the biuret process.

Preferred proteases are those of the subtilisin type. Examples of theseare subtilisins BPN′ and Carlsberg, the protease PB92, the subtilisins147 and 309, the alkaline protease from Bacillus lentus, subtilisin DYand those enzymes of the subtilases no longer however classified in thestricter sense as subtilisines thermitase, proteinase K and theproteases TW3 und TW7. Subtilisin Carlsberg in further developed form isavailable under the trade name Alcalase® from Novozymes A/S, Bagsvaerd,Denmark. Subtilisins 147 and 309 are commercialised under the tradenames Esperase® and Savinase® by the Novozymes company. The variantssold under the name BLAP® are derived from the protease from Bacilluslentus DSM 5483.

Further useable proteases are, for example, those enzymes available withthe trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®,Kannase® and Ovozymes® from the Novozymes Company, those under the tradenames Purafect®, Purafect® OxP and Properase® from Genencor, that underthe trade name Protosol® from Advanced Biochemicals Ltd., Thane, India,that under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd.,China, those under the trade names Proleather® and Protease P® fromAmano Pharmaceuticals Ltd., Nagoya, Japan, and that under thedesignation Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of further useable amylases according to the invention are theα-amylases from Bacillus licheniformis, from B. amyloliquefaciens andfrom B. stearothermophilus, as well as their improved furtherdevelopments for use in detergents and cleaning agents. The enzyme fromB. licheniformis is available from the Novozymes Company under the nameTermamyl® and from the Genencor Company under the name Purastar®ST.Further development products of this α-amylase are available from theNovozymes Company under the trade names Duramyl® and Termamyl® ultra,from the Genencor Company under the name Purastar®OxAm and from DaiwaSeiko Inc., Tokyo, Japan as Keistase®. The α-amylase from B.amyloliquefaciens is commercialised by the Novozymes Company under thename BAN®, and derived variants from the α-amylase from B.stearothermophilus under the names BSG® and Novamyl® also from theNovozymes Company.

Moreover, for these purposes, attention should be drawn to the α-amylasefrom Bacillus sp. A 7-7 (DSM 12368) and thecyclodextrin-glucanotransferase (CGTase) from B. agaradherens (DSM9948).

Moreover, further developments of α-amylase from Aspergillus niger undA. oryzae available from the Company Novozymes under the trade nameFungamyl® are suitable. A further commercial product is the amylase-LT®for example.

According to the invention, lipases or cutinases can also beincorporated, particularly due to their triglyceride cleavingactivities, but also in order to produce in situ peracids from suitablepreliminary steps. These include the available or further developedlipases originating from Humicola lanuginosa (Thermomyces lanuginosus),particularly those with the amino acid substitution D96L. They arecommercialised, for example by the Novozymes Company under the tradenames Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®.Moreover, suitable cutinases, for example are those that were originallyisolated from Fusarium solani pisi and Humicola insolens. Likewiseuseable lipases are available from the Amano Company under thedesignations Lipase CE®, Lipase P®, Lipase B®, and Lipase CES®, LipaseAKG®, Bacillis sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®.Suitable lipases or cutinases whose starting enzymes were originallyisolated from Pseudomonas mendocina und Fusarium solanii are for exampleavailable from Genencor Company. Further important commercial productsthat may be mentioned are the commercial preparations Ml Lipase® undLipomax® originally from Gist-Brocades Company, and the commercialenzymes from the Meito Sangyo KK Company, Japan under the names LipaseMY-30®, Lipase OF® and Lipase PL® as well as the product Lumafast® fromGenencor Company.

In addition, enzymes, which are summarized under the termhemicellulases, can be added. These include, for example mannanases,xanthanlyases, pectinlyases (=pectinases), pectinesterases,pectatlyases, xyloglucanases (=xylanases), pullulanases undβ-glucanases. Suitable mannanases, for example are available under thenames Gamanase® and Pektinex AR® from Novozymes Company, under the namesRohapec® B1L from AB Enzymes and under the names Pyrolase® from DiversaCorp., San. Diego, Calif., USA. β-Glucanase extracted from B. subtilisis available under the name Cereflo® from Novozymes Company.

To increase the bleaching action, oxidoreductases, for example oxidases,oxygenases, katalases, peroxidases, like halo-, chloro-, bromo-,lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases(phenoloxidases, polyphenoloxidases) can be incorporated according tothe invention. Suitable commercial products are Denilite® 1 and 2 fromthe Novozymes Company. Advantageously, additional, preferably organic,particularly preferably aromatic compounds are added that interact withthe enzymes to enhance the activity of the relative oxidoreductases orto facilitate the electron flow (mediators) between the oxidizingenzymes and the stains over strongly different redox potentials.

The enzymes either stem originally from microorganisms, such as thespecies Bacillus, Streptomyces, Humicola, or Pseudomonas, and/or areproduced according to known biotechnological processes using suitablemicroorganisms such as by transgenic expression hosts of the speciesBacillus or filamentary fungi.

Purification of the relevant enzymes follows conveniently usingestablished processes such as precipitation, sedimentation,concentration, filtration of the liquid phases, microfiltration,ultrafiltration, mixing with chemicals, deodorization or suitablecombinations of these steps.

The enzymes can be added in each established form according to the priorart. Included here, for example, are solid preparations obtained bygranulation, extrusion or lyophilization, or particularly for liquidagents or agents in the form of gels, enzyme solutions, advantageouslyhighly concentrated, of low moisture content and/or mixed withstabilizers.

As an alternative application form, the enzymes can also beencapsulated, for example by spray drying or extrusion of the enzymesolution together with a preferably natural polymer or in the form ofcapsules, for example those in which the enzyme is embedded in asolidified gel, or in those of the core-shell type, in which anenzyme-containing core is covered with a water-, air- and/orchemical-impervious protective layer. Further active principles, forexample stabilizers, emulsifiers, pigments, bleaches or colorants can beapplied in additional layers. Such capsules are made using knownmethods, for example by vibratory granulation or roll compaction or byfluid bed processes. Advantageously, these types of granulates, forexample with an applied polymeric film former are dust-free and as aresult of the coating are storage stable.

In addition, it is possible to formulate two or more enzymes together,so that a single granulate exhibits a plurality of enzymatic activities.

A protein and/or enzyme can be protected, particularly in storage,against deterioration such as, for example inactivation, denaturation ordecomposition, for example through physical influences, oxidation orproteolytic cleavage. An inhibition of the proteolysis is particularlypreferred during microbial preparation of proteins and/or enzymes,particularly when the compositions also contain proteases. For this use,inventive agents can comprise stabilizers; the supply of these types ofagents represents a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. For this,benzamidine hydrochloride, borax, boric acids, boronic acids or theirsalts or esters are frequently used, above all derivatives with aromaticgroups, for example ortho, meta or para substituted phenyl boronic acidsor the salts or esters. Ovomucoid and leupeptin, inter alia, arementioned as peptidic protease inhibitors; an additional option is theformation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols like mono-, di-,tri-ethanolamine and -propanolamine and their mixtures, aliphaticcarboxylic acids up to C₁₂, such as, for example succinic acid, otherdicarboxylic acids or salts of the cited acids. End capped alkoxylatedfatty acid amides are also suitable. Certain organic acids used asbuilders can additionally stabilize an included enzyme.

Lower aliphatic alcohols, but above all polyols such as, for exampleglycerol, ethylene glycol, propylene glycol or sorbitol are furtherfrequently used enzyme stabilizers. Likewise, calcium salts are used,such as for example calcium acetate or calcium formate, and magnesiumsalts.

Polyamide oligomers or polymeric compounds like lignin, water-solublevinyl copolymers or cellulose ethers, acrylic polymers and/or polyamidesstabilize enzyme preparations against physical influences or pHvariations. Polymers that contain polyamine-N-oxide are effective enzymestabilizers. Other polymeric stabilizers are the linear C₈-C₁₈polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymaticcomponents of the inventive agents and even increase their performance.Crosslinked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of enzymesagainst oxidative decomposition. A sulfur-containing reducing agent issodium sulfite, for example.

The use of combinations of stabilizers is preferred, for example ofpolyols, boric acid and/or borax, the combination of boric acid orborate, reducing salts and succinic acid or other dicarboxylic acids orthe combination of boric acid or borate with polyols or polyaminocompounds and with reducing salts. The effect of peptide-aldehydestabilizers is increased by the combination with boric acid and/or boricacid derivatives and polyols and still more by the additional effect ofdivalent cations, such as for example calcium ions.

Preferably, one or a plurality of enzymes and/or enzyme preparations,preferably solid protease preparations and/or amylase preparations areincorporated in quantities from 0.1 to 5 wt. %, preferably from 0.2 to4.5 wt. % and in particular from 0.4 to 4 wt. %, each based on the totalenzyme-containing agent.

Disintegration Aids

In order to facilitate the disintegration of the preconditioned moldedbodies, disintegration aids, so-called tablet disintegrators, may beincorporated in the agents to shorten their disintegration times.According to Römpp (9th Edition, Vol. 6, page 4440) and Voigt “Lehrbuchder pharmazeutischen Technologie” (6th Edition, 1987, pages 182-184),tablet disintegrators or disintegration accelerators are auxiliaries,which promote the rapid disintegration of tablets in water or gastricjuices and the release of the pharmaceuticals in an absorbable form.

These substances, which are also known as “disintegrators” by virtue oftheir effect, increase in volume on contact with water so that, firstly,their own volume increases (swelling) and secondly, a pressure can alsobe generated by the release of gases, causing the tablet to disintegrateinto smaller particles. Well-known disintegrators are, for example,carbonate/citric acid systems, although other organic acids may also beused. Swelling disintegration aids are, for example, synthetic polymers,such as polyvinyl pyrrolidone (PVP), or natural polymers and modifiednatural substances, such as cellulose and starch and derivativesthereof, alginates or casein derivatives.

The disintegration aids are preferably incorporated in quantities of 0.5to 10 wt. %, advantageously from 3 to 7 wt. % and especially from 4 to 6wt. %, each based on the total weight of the agent containing thedisintegration aid.

In the context of the present invention, preferred disintegrators thatare used are based on cellulose, and therefore the preferred detergentand cleaning agent compositions comprise such a cellulose-baseddisintegrator in quantities from 0.5 to 10% by weight, advantageously 3to 7% by weight and especially 4 to 6% by weight. Pure cellulose has theformal empirical composition (C₆H₁₀O₅)_(n) and, formally, is aβ-1,4-polyacetal of cellobiose, which, in turn, is made up of twomolecules of glucose. Suitable celluloses consist of ca. 500 to 5000glucose units and, accordingly, have average molecular weights of 50000to 500 000. In the context of the present invention, cellulosederivatives obtainable from cellulose by polymer-analogous reactions mayalso be used as cellulose-based disintegrators. These chemicallymodified celluloses include, for example, products of esterification oretherification reactions in which hydroxy hydrogen atoms have beensubstituted. However, celluloses in which the hydroxy groups have beenreplaced by functional groups that are not attached by an oxygen atommay also be used as cellulose derivatives. The group of cellulosederivatives includes, for example, alkali metal celluloses,carboxymethyl cellulose (CMC), cellulose esters and ethers andaminocelluloses. The cellulose derivatives mentioned are preferably notused on their own, but rather in the form of a mixture with cellulose ascellulose-based disintegrators. The content of cellulose derivatives inmixtures such as these is preferably below 50% by weight and morepreferably below 20% by weight, based on the cellulose-baseddisintegrator. A particularly preferred cellulose-based disintegrator ispure cellulose, free from cellulose derivatives.

The cellulose, used as the disintegration aid, is advantageously notadded in the form of fine particles, but rather conveyed in a coarserform prior to addition to the premix that will be compressed, forexample granulated or compacted. The particle sizes of suchdisintegrators are mostly above 200 μm, advantageously with 90 wt. %between 300 and 1600 μm and particularly at least 90 wt. % between 400and 1200 μm. In the context of the present invention, the abovementionedcoarser disintegration aids, also described in greater detail in thecited publications, are preferred disintegration aids and arecommercially available for example, from the Rettenmaier Company underthe trade name Arbocel® TF-30-HG.

Microcrystalline cellulose can be used as a further cellulose-baseddisintegration aid, or as an ingredient of this component. Themicrocrystalline cellulose is obtained by the partial hydrolysis ofcellulose, under conditions, which only attack and fully dissolve theamorphous regions (ca. 30% of the total cellulosic mass) of thecellulose, leaving the crystalline regions (ca. 70%) intact. Subsequentdisaggregation of the microfine cellulose, obtained by hydrolysis,yields microcrystalline celluloses with primary particle sizes of ca. 5μm and for example, compactable granules with an average particle sizeof 200 μm.

In the context of the present invention, preferred disintegration aids,advantageously a disintegration aid based on cellulose, preferably ingranular, cogranulated or compacted form, are comprised in thedisintegration aid-containing agent in quantities of 0.5 to 10 wt. %,advantageously 3 to 7 wt. % and particularly 4 to 6 wt. %, each based onthe total weight of the disintegration aid-containing agent.

Moreover, according to the invention, it can be preferred to incorporateadditional effervescing systems as the tablet disintegration aids. Thegas-evolving effervescent system can consist of a single substance,which liberates a gas on contact with water. Among these compounds,particular mention is made of magnesium peroxide, which liberates oxygenon contact with water. Normally, however, the gas-liberatingeffervescent system consists of at least two ingredients that react withone another to form gas. Although various possible systems could beused, for example systems releasing nitrogen, oxygen or hydrogen, theeffervescent system used in the detergent tablets according to theinvention should be selected with both economic and ecologicalconsiderations in mind. Preferred effervescent systems consist of alkalimetal carbonate and/or -hydrogen carbonate and an acidifying agentcapable of releasing carbon dioxide from the alkali metal salts inaqueous solution.

Among the alkali metal carbonates or hydrogen carbonates, the sodium andpotassium salts are markedly preferred against the other salts forreasons of cost. Naturally, the relevant pure alkali metal carbonates orhydrogen carbonates need not be used; in fact, mixtures of differentcarbonates and hydrogen carbonates can be preferred.

In preferred effervescent systems, 2 to 20% by weight, advantageously 3to 15% by weight and particularly 5 to 10% by weight of an alkali metalcarbonate or -hydrogen carbonate are used, and 1 to 15, advantageously 2to 12 and preferably 3 to 10% by weight of an acidifying agent, eachbased on the total weight of the agent.

Suitable acidifiers, which liberate carbon dioxide from alkali salts inaqueous solution, are for example, boric acid and alkali metal hydrogensulfates, alkali metal dihydrogen phosphates and other inorganic saltsPreferably, however, organic acidifiers are used, citric acid being thepreferred acidifier. However, solid mono-, oligo- and polycarboxylicacids are also particularly suitable. Within this group, citric acid,tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid,fumaric acid, oxalic acid and polyacrylic acid are again preferred.Organic sulfonic acids, such as amidosulfonic acid, may also be used.Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31%by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33%by weight), is commercially available and may also be used withadvantage as an acidifying agent for the purposes of the presentinvention.

In the context of the present invention, preferred acidifiers in theeffervescing system are from the group of organic di-, tri- andoligocarboxylic acids or their mixtures.

Fragrances

Suitable perfume oils or fragrances include individual perfumecompounds, for example synthetic products of the ester, ether, aldehyde,ketone, alcohol and hydrocarbon type. Perfume compounds of the estertype are, for example, benzyl acetate, phenoxyethyl isobutyrate,p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate,ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallylpropionate and benzyl salicylate. The ethers include, for example,benzyl ethyl ether; the aldehydes include, for example, the linearalkanals containing 8 to 18 carbon atoms, citral, citronellal,citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,lilial and bourgeonal; the ketones include, for example, the ionones,α-isomethyl ionone and methyl cedryl ketone; the alcohols includeanethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcoholand terpineol and the hydrocarbons include, above all, the terpenes,such as limonene and pinene. However, mixtures of various odoriferoussubstances, which together produce an attractive perfume note, arepreferably used. Perfume oils such as these may also contain naturalperfume mixtures obtainable from vegetal sources, for example pine,citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable aremuscatel oil, oil of sage, chamomile oil, clove oil, melissa oil, mintoil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetivertoil, olibanum oil, galbanum oil and ladanum oil and orange blossom oil,neroli oil, orange peel oil and sandalwood oil.

The fragrances may be directly incorporated, although it can also be ofadvantage to apply the fragrances on carriers that due to a slowerfragrance release ensure a long lasting fragrance. Suitable carriermaterials are, for example, cyclodextrins, the cyclodextrin/perfumecomplexes optionally being coated with other auxiliaries.

Colorants

Preferred colorants, which are not difficult for the person skilled inthe art to choose, have high storage stability, are not affected by theother ingredients of the agent or by light and do not have anypronounced substantivity for the substrates such as glass, ceramics orplastic dishes being treated with the colorant-containing agent, so asnot to color them.

1. Solid dishwasher detergent comprising a) 1 to 40 wt. % bleachingagent, b) 0.25 to 20 wt. % non-ionic surfactant(s); c) 0.01 to 10 wt. %of at least one polymer with a molecular weight of 2000 gmol⁻¹ orgreater that possesses at least one positive charge, wherein the weightratio of component b) to component c) is between 25:1 and 100:1. 2-17.(canceled)
 18. The dishwasher detergent of claim 1 wherein the weightratio of the component b) to component c) is between 35:1 and 75:1. 19.The dishwasher detergent of claim 1 comprising 1 to 35 wt. % bleachingagent.
 20. The dishwasher detergent of claim 1 comprising 5 to 15 wt. %bleaching agent.
 21. The dishwasher detergent of claim 1 wherein thebleaching agent is sodium percarbonate.
 22. The dishwasher detergent ofclaim 1 comprising 0.5 to 15 wt. % of one or more non-ionic surfactants.23. The dishwasher detergent of claim 1 comprising 2 to 8 wt. % of oneor more non-ionic surfactants.
 24. The dishwasher detergent of claim 1comprising one or more non-ionic surfactants of the general formulaR¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)CH₂CH(OH)R² in which R¹ stands for alinear or branched aliphatic hydrocarbon group with 4 to 18 carbon atomsor mixtures thereof, R² stands for a linear or branched hydrocarbongroup with 2 to 26 carbon atoms or mixtures thereof, and x stands forvalues between 0.5 and 1.5 and y stands for a value of at least
 15. 25.The dishwasher detergent of claim 1 comprising one or more non-ionicsurfactants of the general formula

in which R¹ stands for a linear or branched, saturated or mono- orpolyunsaturated C₆₋₂₄-alkyl or alkenyl group, each group R² or R³independently of one another is selected from —CH₃, —CH₂CH₃,—CH₂CH₂—CH₃, CH(CH₃)₂, and the indices w, x, y, z independently of oneanother stand for whole numbers from 1 to
 6. 26. The dishwasherdetergent of claim 1 comprising one or more non-ionic surfactants of thegeneral formulaR¹O[CH₂CH(R³)O]_(x)R² in which R¹ stands for linear or branched,saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with1 to 30 carbon atoms, R² stands for linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon groups with 1 to 30carbon atoms, R³ stands for H or a methyl, ethyl, n-propyl, isopropyl,n-butyl, 2-butyl or 2-methyl-2-butyl group, and x has a value between 1and
 40. 27. The general formula of claim 9 wherein either or both R¹ andR² contain 1 to 5 hydroxyl groups.
 28. The general formula of claim 10wherein either or both R¹ and R² are functionalized with an ether group,29. The dishwasher detergent of claim 1 comprising one or more non-ionicsurfactants of the general formulaR¹O[CH₂CH₂O]_(x)CH₂CH(OH)R² which, in addition to a group R¹ that standsfor linear or branched, saturated or unsaturated, aliphatic or aromatichydrocarbon groups with 1 to 30 carbon atoms, additionally comprises alinear or branched, saturated or unsaturated, aliphatic or aromatichydrocarbon group with 1 to 30 carbon atoms R² that is neighboring amonohydroxylated intermediate group —CH₂CH(OH)— and in which x standsfor a number between 1 and
 40. 30. The dishwasher detergent of claim 1comprising one or more non-ionic surfactants of the general formula

in which R¹ and R² independently of one another stand for linear orbranched, saturated or mono- or polyunsaturated hydrocarbon groups with2 to 26 carbon atoms, R³ is selected from —CH₃; —CH₂CH₃, —CH₂CH₂—CH₃,CH(CH₃)₂, and x and y independently stand for values between 1 and 32.31. The general formula of claim 14 wherein the values for x are from 15to 32 and for y are from 0.5 and 1.5.
 32. The dishwasher detergent ofclaim 1 present in the form of a preconditioned unit dose comprisingbetween 0.5 and 4 g non-ionic surfactant.
 33. The dishwasher detergentof claim 1 present in the form of a preconditioned unit dose comprisingbetween 1.5 and 2.5 g non-ionic surfactant.
 34. The dishwasher detergentof claim 1 present in the form of a preconditioned unit dose, whereinsaid preconditioned unit dose comprises a molded body.
 35. The moldedbody of claim 17 wherein the molded body is a multiphase molded body,36. The molded body of claim 17 wherein the molded body is a mono- ormultiphase tablet with a filled cavity.
 37. The dishwasher detergent ofclaim 1 present in the form of a preconditioned unit dose, wherein saidpreconditioned unit dose is selected from the group consisting of afilled water-soluble container, a filled injection molded body, a filledcast body and a filled film pouch.
 38. The dishwasher detergent of claim1 comprising 0.02 to 7.5 wt. % of at least one polymer with a molecularweight of 2000 gmol⁻¹ or above that possesses at least one positivecharge.
 39. The dishwasher detergent of claim 1 comprising 0.1 to 1 wt.% of at least one polymer with a molecular weight of 2000 gmol⁻¹ orabove that possesses at least one positive charge.
 40. The dishwasherdetergent of claim 1 wherein the polymer c) possesses monomer units ofthe formula R¹R²C═CR³R⁴, in which each group R¹, R², R³, R⁴independently is selected from hydrogen, derivatized hydroxyl groups, C1to C30 linear or branched alkyl groups, aryl, aryl substituted C1-30linear or branched alkyl groups, polyalkoxylated alkyl groups,heteroatomic organic groups having at least one positive charge withoutcharged nitrogen, at least one quaternized nitrogen atom or at least oneamino group with a positive charge in the pH range 2 to 11, or saltsthereof, with the proviso that at least one group R¹, R², R³, R⁴ is aheteroatomic organic group with at least one positive charge withoutcharged nitrogen, at least one quaternized nitrogen atom or at least oneamino group with a positive charge.
 41. The dishwasher detergent ofclaim 1 wherein the polymer c) comprises at least one ofdiallyldimethylammonium salts or acrylamidopropyltrimethylammonium saltsas monomer units.
 42. The dishwasher detergent of claim 1 wherein theproportion by weight of the component b) to the component c) is between25:1 and 100:1.
 43. The dishwasher detergent of claim 1 wherein theproportion by weight of the component b) to the component c) is between35:1 and 70:1.
 44. The dishwasher detergent of claim 1 comprising 10 to80 wt. % of one or more water-soluble builders.
 45. The dishwasherdetergent of claim 1 comprising 25 to 65 wt. % of one or morewater-soluble builders.
 46. A method of cleaning glassware comprisingcontacting the glassware with the dishwasher detergent of claim 1, thenrinsing the glassware.